Sample records for gas phase silanization

  1. Thermal reactor. [liquid silicon production from silane gas (United States)

    Levin, H.; Ford, L. B. (Inventor)


    A thermal reactor apparatus and method of pyrolyticaly decomposing silane gas into liquid silicon product and hydrogen by-product gas is disclosed. The thermal reactor has a reaction chamber which is heated well above the decomposition temperature of silane. An injector probe introduces the silane gas tangentially into the reaction chamber to form a first, outer, forwardly moving vortex containing the liquid silicon product and a second, inner, rewardly moving vortex containing the by-product hydrogen gas. The liquid silicon in the first outer vortex deposits onto the interior walls of the reaction chamber to form an equilibrium skull layer which flows to the forward or bottom end of the reaction chamber where it is removed. The by-product hydrogen gas in the second inner vortex is removed from the top or rear of the reaction chamber by a vortex finder. The injector probe which introduces the silane gas into the reaction chamber is continually cooled by a cooling jacket.

  2. 76 FR 88 - Grant of Authority for Subzone Status, REC Silicon (Polysilicon and Silane Gas), Moses Lake... (United States)


    ... Foreign-Trade Zones Board Grant of Authority for Subzone Status, REC Silicon (Polysilicon and Silane Gas... special-purpose subzone at the polysilicon and silane gas manufacturing facility of REC Silicon, located... silane gas at the facilities of REC Silicon, located in Moses Lake, Washington (Subzone 203B), as...

  3. A silane-based polysilicon process (United States)

    Grayson, P. E.; Jaffe, J.


    A silane based polysilicon process plant was constructed in Miami, Oklahoma. The processes included: the synthesis of crude silane gas, ultrapurification of the gas, and direct pyrolysis to product silicon. Features of the process provided for direct continuous operation from process feed to final product, without the requirement to store intermediates or even convert the silane to a liquid phase. Semiconductor product quality as analyzed internally was demonstrated by the first integrated operation of the plant.

  4. Analysis of Gas Membrane Ultra-High Purification of Small Quantities of Mono-Isotopic Silane

    Energy Technology Data Exchange (ETDEWEB)

    de Almeida, Valmor F [ORNL; Hart, Kevin J [ORNL


    A small quantity of high-value, crude, mono-isotopic silane is a prospective gas for a small-scale, high-recovery, ultra-high membrane purification process. This is an unusual application of gas membrane separation for which we provide a comprehensive analysis of a simple purification model. The goal is to develop direct analytic expressions for estimating the feasibility and efficiency of the method, and guide process design; this is only possible for binary mixtures of silane in the dilute limit which is a somewhat realistic case. Among the common impurities in crude silane, methane poses a special membrane separation challenge since it is chemically similar to silane. Other potential problematic surprises are: ethylene, diborane and ethane (in this order). Nevertheless, we demonstrate, theoretically, that a carefully designed membrane system may be able to purify mono-isotopic, crude silane to electronics-grade level in a reasonable amount of time and expenses. We advocate a combination of membrane materials that preferentially reject heavy impurities based on mobility selectivity, and light impurities based on solubility selectivity. We provide estimates for the purification of significant contaminants of interest. To improve the separation selectivity, it is advantageous to use a permeate chamber under vacuum, however this also requires greater control of in-leakage of impurities in the system. In this study, we suggest cellulose acetate and polydimethylsiloxane as examples of membrane materials on the basis of limited permeability data found in the open literature. We provide estimates on the membrane area needed and priming volume of the cell enclosure for fabrication purposes when using the suggested membrane materials. These estimates are largely theoretical in view of the absence of reliable experimental data for the permeability of silane. Last but not least, future extension of this work to the non-dilute limit may apply to the recovery of silane from

  5. Silane based coating of aluminium mold

    DEFF Research Database (Denmark)


    A method of preparing an aluminum mold for injection molding is provided, the method comprises the steps of providing an aluminum mold having a least one surface, subjecting the at least one surface to a gas or liquid phase silane to thereby form an anti-stiction coating, the anti-stiction coating...... comprising a chemically bonded monolayer of silane compounds on the at least one surface wherein the silane is a halogenated silane. The at least one surface coated with the anti-stiction coating may be configured to withstand an injection molding process at a pressure above 100 MPa. Furthermore, a mold...... having at least one closed cavity is provided, at least one surface of the at least one cavity being an aluminium surface coated with a silane based coating layer. The silane based anti-stiction coating improves the anti-stiction properties of the mold which may allow for molding and demolding...

  6. Formation of Higher Silanes in Low-Temperature Silane (SiH4) Ices. (United States)

    Tarczay, György; Förstel, Marko; Maksyutenko, Pavlo; Kaiser, Ralf I


    A novel approach for the synthesis and identification of higher silanes (SinH2n+2, where n ≤ 19) is presented. Thin films of (d4-)silane deposited onto a cold surface were exposed under ultra-high-vacuum conditions to energetic electrons and sampled on line and in situ via infrared and ultraviolet-visible spectroscopy. Gas phase products released by fractional sublimation in the warm-up phase after the irradiation were probed via a reflectron time-of-flight mass spectrometer coupled with a tunable vacuum ultraviolet photon ionization source. The formation mechanisms of (higher) silanes were investigated by irradiating codeposited 1:1 silane (SiH4)/d4-silane (SiD4) ices, suggesting that both radical-radical recombination and radical insertion pathways contribute to the formation of disilane along with higher silanes up to nonadecasilane (Si19H40).

  7. Colloidal assemblies on patterned silane layers (United States)

    Jonas, Ulrich; del Campo, Aránzazu; Krüger, Christian; Glasser, Gunnar; Boos, Diana


    The site-selective assembly of colloidal polymer particles onto laterally patterned silane layers was studied as a model system for the object assembly process at mesoscale dimensions. The structured silane monolayers on silicon oxide substrates were fabricated by a combination of liquid- and gas-phase deposition of different trialkoxysilanes with a photolithographic patterning technique. By using this method various types of surface functionalizations such as regions with amino functions next to areas of the bare silica surface or positively charged regions of a quaternary ammonium silane surrounded by a hydrophobic octadecylsilane film could be obtained. Furthermore, a triethoxysilane with a photoprotected amino group was synthesized, which allowed direct photopatterning after monolayer preparation, leading to free NH2 groups at the irradiated regions. The different silane monolayer patterns were used to study the surface assembly behavior of carboxylated methacrylate particles by optical and scanning electron microscopy. In dependence of the assembly conditions (different surface functionalizations, pH, and drying conditions), a selective preference of the particles for a specific surface type versus others was found. Site-specific colloid adsorption could be observed also on the photosensitive silane layers after local deprotection with light. From the photosensitive silane and positively charged ammonium silane, molecularly mixed monolayers were prepared, which allowed particle adsorption and photoactivation within the same monolayer as shown by fluorescence labeling. PMID:11959954

  8. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T


    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

  9. Numerical study of the effect of gas temperature on the time for onset of particle nucleation in argon-silane low-pressure plasmas

    CERN Document Server

    Bhandarkar, U; Girshick, S L


    Particle nucleation in silane plasmas has attracted interest for the past decade, both due to the basic problems of plasma chemistry involved and the importance of silane plasmas for many applications. A better understanding of particle nucleation may facilitate the avoidance of undesirable particle contamination as well as enable the controlled production of nanoparticles for novel applications. While understanding of particle nucleation has significantly advanced over the past years, a number of questions have not been resolved. Among these is the delay of particle nucleation with an increasing gas temperature, which has been observed in experiments in argon-silane plasmas. We have developed a quasi-one-dimensional model to simulate particle nucleation and growth in silane containing plasmas. In this paper we present a comparative study of the various effects that have been proposed as explanations for the nucleation delay. Our results suggest that the temperature dependence of the Brownian diffusion coeffi...

  10. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T


    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

  11. Gas-Phase Thermolyses

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge


    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......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...

  12. Gas phase pulse radiolysis

    International Nuclear Information System (INIS)

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


    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

  13. Silane Modification of Cellulose Acetate Dense Films as Materials for Acid Gas Removal

    KAUST Repository

    Achoundong, Carine S. K.


    The modification of cellulose acetate (CA) films via grafting of vinyltrimethoxysilane (VTMS) to -OH groups, with subsequent condensation of hydrolyzed methoxy groups on the silane to form a polymer network is presented. The technique is referred to as GCV-modification. The modified material maintains similar H2S/CH4 and CO2/CH 4 selectivities compared to the unmodified material; however the pure CO2 and H2S permeabilities are 139 and 165 barrers, respectively, which are more than an order of magnitude higher than the neat polymer. The membranes were tested at feed pressures of up to 700 psia in a ternary 20 vol. %H2S/20 vol. % CO2/60 vol. % CH 4 mixture. Even under aggressive feed conditions, GCV-modified CA showed comparable selectivities and significantly higher permeabilities. Furthermore, GCV-modified membrane had a lower Tg, lower crystallinity, and higher flexibility than neat CA. The higher flexibility is due to the vinyl substituent provided by VTMS, thereby reducing brittleness, which could be helpful in an asymmetric membrane structure. © 2013 American Chemical Society.

  14. Silane in IRC +10216 (United States)

    Goldhaber, D. M.; Betz, A. L.


    Silane has been detected in the gas surrounding IRC +10216. Thirteen absorption lines in the nu-4 band around 917/cm were observed at 0.2 km/s resolution. A lower limit to the radial column density is 2 x 10 to the 15th/sq cm, and the relative strengths of the transitions indicate an average rotational temperature of 173 K.

  15. Gas-phase chemical dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Weston, R.E. Jr.; Sears, T.J.; Preses, J.M. [Brookhaven National Laboratory, Upton, NY (United States)


    Research in this program is directed towards the spectroscopy of small free radicals and reactive molecules and the state-to-state dynamics of gas phase collision, energy transfer, and photodissociation phenomena. Work on several systems is summarized here.

  16. Determination of Xylene and Toluene by Solid-Phase Microextraction Using Au Nanoparticles-Thiol Silane Film Coupled to Ion Mobility Spectrometry. (United States)

    Allafchian, Ali Reza; Akhgar, Ava; Ielbeigi, Vahideh; Tabrizchi, Mahmoud


    A simple, rapid and sensitive method for analysis of xylene and toluene was developed using the solid-phase microextraction (SPME) combined with ion mobilityspectrometry (IMS). Gold nanoparticles-thiol silane film (Au NPs-TSF) was applied as a newsorbent for SPME. Thiol silane film was formed on the surface of a stainless steel wire through incorporating Au nanoparticles during synthesis using sol-gel technique. The extraction properties of the fiber to xylene and toluene were examined, using a SPME device and thermal desorption ininjection port of IMS. The calibration graphs were linear in the range of 1.10-32.0 and 16.0-112.0 ppb for xylene and toluene, respectively. The detection limits for xylene and toluene were 0.7 and 8.0 ppb, respectively. The proposed method was applied without any considerable sample pretreatment and it was found to be simple enough to be strongly recommended for real sample analysis.

  17. Effect of amine counterion type on the retention of basic compounds on octadecyl silane bonded silica-based and polybutadiene-coated zirconia phases. (United States)

    Yang, Xiqin; Dai, Jun; Carr, Peter W


    In a previous paper, we compared the mixed-mode retention characteristics of cationic solutes on octadecyl silane-bonded silica (ODS) and polybutadiene-coated zirconia (PBD-ZrO2) phases. It is well recognized that both reversed-phase and ion-exchange interactions contribute to the retention of cations on ODS phases. The reversed-phase interaction results from the bonded hydrocarbon chain; the ion-exchange interaction originates in the ionized residual silanol groups. These two types of interactions also exist on the PBD-ZrO2 phase. The polybutadiene contributes to the reversed-phase interaction and the ionized zirconol, but primarily, the adsorbed Lewis base anions, such as phosphate or fluoride, contribute to the ion-exchange interaction. We have shown that on ODS phases, reversed-phase interactions are much more important, whereas the opposite is true of PBD-ZrO2 phases. In this work, we investigate the effect of several amine mobile phase counterions on the retention of cationic solutes on ODS and PBD-ZrO2 phases. The effects of the chain length and the type of amine (1 degree, 2 degrees, 3 degrees) counterion on the retention of basic compounds were studied. In contrast to older studies of type A silica-based phases, the results show that the chain length and type of the amine blocker do not have a large effect on the retention of basic compounds with the newer type B silica-based materials. However, on the PBD-ZrO2 phase, very striking differences in retention were observed with different amine counterions. We show that the molecular geometry of the amine counterion has a significant effect on the retention of basic solutes on the PBD-ZrO2 phase.

  18. Modeling of gas-phase chemistry in the chemical vapor deposition of polysilicon in a cold wall system

    Energy Technology Data Exchange (ETDEWEB)

    Toprac, A.J.; Edgar, T.F.; Trachtenberg, I. (Univ. of Texas, Austin, TX (United States). Dept. of Chemical Engineering)


    The relative contribution of gas-phase chemistry to deposition processes is an important issue both from the standpoint of operation and modeling of these processes. In polysilicon deposition from thermally activated silane in a cold wall rapid thermal chemical vapor deposition (RTCVD) system, the relative contribution of gas-phase chemistry to the overall deposition rate was examined by a mass-balance model. Evaluating the process at conditions examined experimentally, the model indicated that gas-phase reactions may be neglected to good accuracy in predicting polysilicon deposition rate. The model also provided estimates of the level of gas-phase generated SiH[sub 2] associated with deposition on the cold-process chamber walls.

  19. Iodine removal from a gas phase

    International Nuclear Information System (INIS)

    Vikis, A. Ch.


    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)

  20. Iodine removal from a gas phase

    International Nuclear Information System (INIS)

    Vikis, A.C.


    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

  1. Effect of silane concentration on the supersonic combustion of a silane/methane mixture (United States)

    Northam, G. B.; Mclain, A. G.; Pellett, G. L.; Diskin, G. S.


    A series of direct connect combustor tests was conducted to determine the effect of silane concentration on the supersonic combustion characteristics of silane/methane mixtures. Shock tube ignition delay data indicated more than an order of magnitude reduction in ignition delay times for both 10 and 20 percent silane/methane mixtures as compared to methane. The ignition delay time of the 10 percent mixture was only a factor of 2.3 greater than that of the 20 percent mixture. Supersonic combustion tests were conducted with the fuel injected into a model scramjet combustor. The combustor was mounted at the exit of a Mach 2 nozzle and a hydrogen fired heater was used to provide a variation in test gas total temperature. Tests using the 20 percent silane/methane mixture indicated considerable combustion enhancement when compared to methane alone. This mixture had an autoignition total temperature of 1650 R. This autoignition temperature can be contrasted with 2330 R for hydrogen and 1350 R for a 20 percent silane/hydrogen mixture in similar hardware. Methane without the silane additive did not autoignite in this configuration at total temperatures as high as 3900 R, the maximum temperature at which tests were conducted. Supersonic combustion tests with the silane concentration reduced to 10 percent indicated little improvement in combustion performance over pure methane. The addition of 20 percent silane to methane resulted in a pyrophoric fuel with good supersonic combustion performance. Reducing the silane concentration below this level, however, yielded a less pyrophoric fuel that exhibited poor supersonic combustion performance.

  2. Rate processes in gas phase

    International Nuclear Information System (INIS)

    Hansen, C.F.


    Reaction-rate theory and experiment are given a critical review from the engineers' point of view. Rates of heavy-particle, collision-induced reaction in gas phase are formulated in terms of the cross sections and activation energies of the reaction. The effect of cross section function shape and of excited state contributions to the reaction both cause the slope of Arrhenius plots to differ from the true activation energy, except at low temperature. The master equations for chemically reacting gases are introduced, and dissociation and ionization reactions are shown to proceed primarily from excited states about kT from the dissociation or ionization limit. Collision-induced vibration, vibration-rotation, and pure rotation transitions are treated, including three-dimensional effects and conservation of energy, which have usually been ignored. The quantum theory of transitions at potential surface crossing is derived, and results are found to be in fair agreement with experiment in spite of some questionable approximations involved

  3. Phase transition in the hadron gas model

    International Nuclear Information System (INIS)

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


    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

  4. Condensed phase decomposition and gas phase combustion of hydrazinium nitroformate

    NARCIS (Netherlands)

    Dragomir, O.E.; Tummers, M.J.; Veen, E.H. van; Heijden, A.E.D.M. van der; Roekaerts, D.J.E.M.


    This paper presents the results of a series of experiments on the condensed phase decomposition and the gas phase combustion of hydrazinium nitroformate (HNF). The experiments include SEM analysis of quenched samples that showed evidence of the formation of a foam layer. FTIR spectrometry and mass

  5. Silane-Pyrolysis Reactor With Nonuniform Heating (United States)

    Iya, Sridhar K.


    Improved reactor serves as last stage in system processing metallurgical-grade silicon feedstock into silicon powder of ultrahigh purity. Silane pyrolized to silicon powder and hydrogen gas via homogeneous decomposition reaction in free space. Features set of individually adjustable electrical heaters and purge flow of hydrogen to improve control of pyrolysis conditions. Power supplied to each heater set in conjunction with flow in reactor to obtain desired distribution of temperature as function of position along reactor.

  6. Degree of dissociation measured by FTIR absorption spectroscopy applied to VHF silane plasmas

    International Nuclear Information System (INIS)

    Sansonnens, L.; Howling, A.A.; Hollenstein, C.


    In situ Fourier transform infrared (FTIR) absorption spectroscopy has been used to determine the fractional depletion of silane in a radio-frequency (rf) glow discharge. The technique used a simple single pass arrangement and was implemented in a large area industrial reactor for deposition of amorphous silicon. Measurements were made on silane plasmas for a range of excitation frequencies. It was observed that at constant plasma power, the fractional depletion increased from 35% at 13.56 MHz to 70% at 70 MHz. With a simple model based on the density continuity equations in the gas phase, it was shown that this increase is due to a higher dissociation rate and is largely responsible for the observed increase in the deposition rate with the frequency. (author) 5 figs., 30 refs

  7. Gas-Phase Infrared; JCAMP Format (United States)

    SRD 35 NIST/EPA Gas-Phase Infrared; JCAMP Format (PC database for purchase)   This data collection contains 5,228 infrared spectra in the JCAMP-DX (Joint Committee for Atomic and Molecular Physical Data "Data Exchange") format.

  8. Determination of NH{sub 2} concentration on 3-aminopropyl tri-ethoxy silane layers and cyclopropylamine plasma polymers by liquid-phase derivatization with 5-iodo 2-furaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Manakhov, Anton, E-mail: [National University of Science and Technology “MISiS”, Leninsky pr. 4, Moscow 119049 (Russian Federation); RG Plasma Technologies, CEITEC—Central European Institute of Technology, Masaryk University, Kotlářská, 2, 61137 Brno (Czech Republic); Čechal, Jan [CEITEC—Central European Institute of Technology, Brno University of Technology, Purkyňova 123, 612 00 Brno (Czech Republic); Institute of Physical Engineering, Brno University of Technology, Technická 2896/2, 616 69 Brno (Czech Republic); Michlíček, Miroslav [RG Plasma Technologies, CEITEC—Central European Institute of Technology, Masaryk University, Kotlářská, 2, 61137 Brno (Czech Republic); Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, 61137 Brno (Czech Republic); Shtansky, Dmitry V. [National University of Science and Technology “MISiS”, Leninsky pr. 4, Moscow 119049 (Russian Federation)


    Highlights: • A new method for primary amines derivatization is proposed and validated. • The chemical structure of APTES layer is studied. • The derivatization by 5-iodo 2-furaldehyde allowed to avoid side reactions in contrast to 4-trifluoromethyl benzaldehyde derivatization. - Abstract: The quantification of concentration of primary amines, e.g. in plasma polymerized layers is a very important task for surface analysis. However, the commonly used procedure, such as gas phase derivatization with benzaldehydes, shows several drawbacks, the most important of which are the side reaction effects. In the present study we propose and validate a liquid phase derivatization using 5-iodo 2-furaldehyde (IFA). It was demonstrated that the content of NH{sub 2} groups can be determined from the atomic concentrations measured by X-ray photoelectron spectroscopy (XPS), in particular from the ratio of I 3d and N 1s peak intensities. First, we demonstrate the method on a prototypical system such as 3-aminopropyl tri-ethoxy silane (APTES) layer. Here the XPS analysis carried out after reaction of APTES layer with IFA gives the fraction of primary amines (NH{sub 2}/N) of 38.3 ± 7.9%. Comparing this value with that obtained by N 1s curve fitting of APTES layer giving 40.9 ± 9.5% of amine groups, it can be concluded that all primary amines were derivatized by reaction with IFA. The second system to demonstrate the method comprises cyclopropylamine (CPA) plasma polymers that were free from conjugated imines. In this case the method gives the NH{sub 2} fraction ∼8.5%. This value is closely matching the NH{sub 2}/N ratio estimated by 4-trifluoromethyl benzaldehyde (TFBA) derivatization. The reaction of IFA with CPA plasma polymer exhibiting high density of conjugated imines revealed the NH{sub 2}/N fraction of ∼10.8%. This value was significantly lower compared to 17.3% estimated by TFBA derivatization. As the overestimated density of primary amines measured by TFBA

  9. Hydrolysierbare und polymerisierbare Silane


    Wolter, H.; Schmitzer, S.


    WO 200053612 A UPAB: 20001117 NOVELTY - Hydrolyzable and polymerizable organosilicon compounds with unsaturated carboxylic acid amide groups attached to silicon via the amide nitrogen and organic linking groups. DETAILED DESCRIPTION - Hydrolyzable and polymerizable, organically-modified silanes of formula (I). B = a 2-50C organic residue with at least one C=C double bond, which is attached to the -CONH- group via a carbon atom and contains no norbornene, bicyclo(2.2.2)oct-2-ene or 7-oxa-bicyc...

  10. Rocket Ignition Demonstrations Using Silane (United States)

    Pal, Sibtosh; Santoro, Robert; Watkins, William B.; Kincaid, Kevin


    Rocket ignition demonstration tests using silane were performed at the Penn State Combustion Research Laboratory. A heat sink combustor with one injection element was used with gaseous propellants. Mixtures of silane and hydrogen were used as fuel, and oxygen was used as oxidizer. Reliable ignition was demonstrated using fuel lead and and a swirl injection element.

  11. Two-dimensional high-performance thin-layer chromatography of tryptic bovine albumin digest using normal- and reverse-phase systems with silanized silica stationary phase. (United States)

    Gwarda, Radosław Łukasz; Dzido, Tadeusz Henryk


    Among many advantages of planar techniques, two-dimensional (2D) separation seems to be the most important for analysis of complex samples. Here we present quick, simple and efficient two-dimensional high-performance thin-layer chromatography (2D HPTLC) of bovine albumin digest using commercial HPTLC RP-18W plates (silica based stationary phase with chemically bonded octadecyl ligands of coverage density 0.5μmol/m(2) from Merck, Darmstadt). We show, that at low or high concentration of water in the mobile phase comprised methanol and some additives the chromatographic systems with the plates mentioned demonstrate normal- or reversed-phase liquid chromatography properties, respectively, for separation of peptides obtained. These two systems show quite different separation selectivity and their combination into 2D HPTLC process provides excellent separation of peptides of the bovine albumin digest. Copyright © 2013 Elsevier B.V. All rights reserved.

  12. Gas phase equilibrium structure of histamine. (United States)

    Tikhonov, Denis S; Rykov, Anatolii N; Grikina, Olga E; Khaikin, Leonid S


    The first gas electron diffraction (GED) experiment for histamine was carried out. The equilibrium structure of histamine in the gas phase was determined on the basis of the data obtained. The refinement was also supported by the rotational constants obtained in previous studies [B. Vogelsanger, et al., J. Am. Chem. Soc., 1991, 113, 7864-7869; P. Godfrey, et al., J. Am. Chem. Soc., 1998, 120, 10724-10732] and quantum chemical calculations. The proposed mechanism of tautomerization by simultaneous intermolecular transfer of hydrogens in a histamine dimer helps to explain the distribution of tautomers in different experiments. The estimations of the conformational interconversion times provided the explanation for the absence of some conformers in the rotational spectroscopy experiments.

  13. Gas phase thermochemistry of organogermanium compounds

    Energy Technology Data Exchange (ETDEWEB)

    Engel, John P. [Iowa State Univ., Ames, IA (United States)


    A variety of silyl- and alkyl-germylene precursors have been synthesized and subsequently pyrolyzed in the gas phase. Arrhenius parameters were obtained employing a pulsed-stirred flow reactor for these unimolecular decompositions. These precursors are divided into two major categories by mechanism of germylene extrusion: α-elimination precursors and germylacetylenes. The extrusion of germylenes from germylacetylene precursors is of primary interest. A mechanism is proposed employing a germacyclopropene intermediate. Evidence supporting this mechanism is presented. In the process of exploring germylacetylenes as germylene precursors, an apparent dyatropic rearrangement between germanium and silicon was observed. This rearrangement was subsequently explored.

  14. Gas phase reactive collisions, experimental approach

    Directory of Open Access Journals (Sweden)

    Canosa A.


    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.

  15. Vaccum Gas Tungsten Arc Welding, phase 1 (United States)

    Weeks, J. L.; Krotz, P. D.; Todd, D. T.; Liaw, Y. K.


    This two year program will investigate Vacuum Gas Tungsten Arc Welding (VGTAW) as a method to modify or improve the weldability of normally difficult-to-weld materials. VGTAW appears to offer a significant improvement in weldability because of the clean environment and lower heat input needed. The overall objective of the program is to develop the VGTAW technology and implement it into a manufacturing environment that will result in lower cost, better quality and higher reliability aerospace components for the space shuttle and other NASA space systems. Phase 1 of this program was aimed at demonstrating the process's ability to weld normally difficult-to-weld materials. Phase 2 will focus on further evaluation, a hardware demonstration and a plan to implement VGTAW technology into a manufacturing environment. During Phase 1, the following tasks were performed: (1) Task 11000 Facility Modification - an existing vacuum chamber was modified and adapted to a GTAW power supply; (2) Task 12000 Materials Selection - four difficult-to-weld materials typically used in the construction of aerospace hardware were chosen for study; (3) Task 13000 VGTAW Experiments - welding experiments were conducted under vacuum using the hollow tungsten electrode and evaluation. As a result of this effort, two materials, NARloy Z and Incoloy 903, were downselected for further characterization in Phase 2; and (4) Task 13100 Aluminum-Lithium Weld Studies - this task was added to the original work statement to investigate the effects of vacuum welding and weld pool vibration on aluminum-lithium alloys.

  16. Phase transitions in a gas of anyons

    International Nuclear Information System (INIS)

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


    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.

  17. From molecules to particles in silane plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Howling, A.A.; Courteille, C.; Dorier, J.L.; Sansonnier, L.; Hollenstein, C. [Ecole Polytechnique Federale, Lausanne (Switzerland). Centre de Recherche en Physique des Plasma (CRPP)


    Particle formation has been investigated experimentally from the initial molecular precursor up to the final micron-sized particles in a low pressure silane rf capacity discharge. Neutrals and ions were studied by quadrupole mass spectrometry in power-modulated plasmas: Whole series of negative ions were observed, ranging from monosilicon anions through to nanometric clusters. Anion confinement results in particles and conversely, anion de-trapping can inhibit particle formation. Plasma polymerisation is considered in terms of neutral and ionic species. Laser light scattering measurements show that particles appear during a rapid coalescence phase and possible mechanisms are discussed. (author) 5 figs., 28 refs.

  18. Resolving Gas-Phase Metallicity In Galaxies (United States)

    Carton, David


    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

  19. High-temperature Superconductivity in compressed Solid Silane (United States)

    Zhang, Huadi; Jin, Xilian; Lv, Yunzhou; Zhuang, Quan; Liu, Yunxian; Lv, Qianqian; Bao, Kuo; Li, Da; Liu, Bingbing; Cui, Tian


    Crystal structures of silane have been extensively investigated using ab initio evolutionary simulation methods at high pressures. Two metallic structures with P21/c and C2/m symmetries are found stable above 383 GPa. The superconductivities of metallic phases are fully explored under BCS theory, including the reported C2/c one. Perturbative linear-response calculations for C2/m silane at 610 GPa reveal a high superconducting critical temperature that beyond the order of 102 K. PMID:25746861

  20. 40 CFR 721.9507 - Polyester silane. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polyester silane. 721.9507 Section 721... Polyester silane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a polyester silane (P-95-1022) is subject to reporting under this section for the...

  1. Airborne Multi-Gas Sensor, Phase II (United States)

    National Aeronautics and Space Administration — Mesa Photonics has developed laser-based gas sensor technology compatible with UAV deployment. Our Airborne MUlti-Gas Sensor (AMUGS) technology is based upon...

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

    NARCIS (Netherlands)

    Daftaribesheli, Majid


    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

  3. Direct silanization of zirconia for increased biointegration. (United States)

    Caravaca, Carlos; Shi, Liu; Balvay, Sandra; Rivory, Pascaline; Laurenceau, Emmanuelle; Chevolot, Yann; Hartmann, Daniel; Gremillard, Laurent; Chevalier, Jérôme


    High-performance bioinert ceramics such as zirconia have been used for biomedical devices since the early seventies. In order to promote osseointegration, the historical solution has been to increase the specific surface of the implant through roughness. Nevertheless these treatments on ceramics may create defects at the surface, exposing the material to higher chances of early failure. In zirconia, such treatments may also affect the stability of the surface. More recently, the interest of improving osseointegration of implants has moved the research focus towards the actual chemistry of the surface. Inspired by this, we have adapted the current knowledge and techniques of silica functionalization and applied it to successfully introduce 3-aminopropyldimethylethoxy silane (APDMES) directly on the surface of zirconia (3Y-TZP). We used plasma of oxygen to clean the surface and promote hydroxylation of the surface to increase silane density. The samples were extensively characterized by means of X-ray photoelectron spectroscopy (XPS) and contact angle, mechanically tested and its cytotoxicity was evaluated through cell adhesion and proliferation tests. Additionally, aging was studied to discard negative effects of the treatment on the stability of the tetragonal phase. No adverse effect was found on the mechanical response of treated samples. In addition, plasma-treated samples exhibited an unexpectedly higher resistance to aging. Finally, silane density was 35% lower than the one reported in literature for silica. However cells displayed a qualitatively higher spreading in opposition to the rounder appearance of cells on untreated zirconia. These results lay the foundations for the next generation of zirconia implants with biologically friendlier surfaces. The use of zirconia-based ceramics in biomedical devices is broad and well accepted, especially in dental implants. However, they do not bond naturally to bone, therefore to ensure fixation surgeons typically rely

  4. Carbon Nanotube Gas Sensor, Phase I (United States)

    National Aeronautics and Space Administration — Sensing gas molecules is critical to environmental monitoring, control of chemical processes, space missions as well as agricultural and medical applications....

  5. Active Gas Regenerative Liquefier, Phase I (United States)

    National Aeronautics and Space Administration — We offer a novel liquefier that has the potential to simultaneously increase thermodynamic efficiency and significantly reduce complexity. The ?active gas...

  6. Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2 (United States)

    Dickson, C. R.; Gould, R. K.; Felder, W.


    High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

  7. The nature of ionic liquids in the gas phase. (United States)

    Leal, João P; Esperança, José M S S; da Piedade, Manuel E Minas; Lopes, José N Canongia; Rebelo, Luís P N; Seddon, Kenneth R


    Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) experiments showed that when aprotic ionic liquids vaporize under pressure and temperature conditions similar to those of a reduced-pressure distillation, the gas phase is composed of discrete anion-cation pairs. The evolution of the mass spectrometric signals recorded during fractional distillations of binary ionic liquid mixtures allowed us to monitor the changes of the gas-phase composition and the relative volatility of the components. In addition, we have studied a protic ionic liquid, and demonstrated that it exists as separated neutral molecules in the gas phase.

  8. Residence time distribution of the gas phase in a mechanically agitated gas-liquid reactor

    NARCIS (Netherlands)

    Thijert, M.P.G.; Oyevaar, M.H.; Kuper, W.J.; Westerterp, K.R.


    In this study we present a measuring method and extensive experimental data on the gas phase RTD in a mechanically agitated gas-liquid reactor with standard dimensions over a wide range of superficial gas velocities, agitation rates and agitator sizes. The results are modelled successfully, using

  9. New Liquid Phases for the Gas Chromatographic Separation of Strong Bases on Capillary Columns


    Grob, K.


    The current practice of pretreating the solid support with free alkali to increase separation efficiency for basic compounds proved to be unsuitable for capillary columns. Instead of this, homogenous organic materials of high base strength are required. We found polyethylene imine (PEI) and polypropylene imine (PPI) to be very efficient as liquid phases of capillary columns for the separation of bases. The preparation of polymers is mentioned. Silanization or acetylation of the free hydroxyl ...

  10. Airborne Multi-Gas Sensor, Phase I (United States)

    National Aeronautics and Space Administration — Mesa Photonics proposes to develop an Airborne Multi-Gas Sensor (AMUGS) based upon two-tone, frequency modulation spectroscopy (TT-FMS). Mesa Photonics has developed...

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

    DEFF Research Database (Denmark)

    Østberg, Martin


    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...... of the mixing in the SNR process using injection of NH3 with carrier gas into the flue gas in crossflow by a quartz nozzle.Experiments were made with variation in NH3 flow, carrier gas flow, carrier gas composition (O2 concentration) and reactor temperature. Natural gas has been used as an addition...

  12. Headspace Solid-Phase Microextraction Coupled with Gas ...

    African Journals Online (AJOL)

    contact temperature measurement system (ONTMS). Headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry (GC-MS) was used to analyze the volatile composition of raw FCP and its various ...

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

    National Research Council Canada - National Science Library

    Locke, B


    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

    National Research Council Canada - National Science Library

    LOCKE, B


    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. Ionization of Gas-Phase Polycyclic Aromatic Hydrocarbons in Electrospray Ionization Coupled with Gas Chromatography. (United States)

    Cha, Eunju; Jeong, Eun Sook; Han, Sang Beom; Cha, Sangwon; Son, Junghyun; Kim, Sunghwan; Oh, Han Bin; Lee, Jaeick


    Herein, gas-phase polycyclic aromatic hydrocarbons (PAHs) as nonpolar compounds were ionized to protonated molecular ions [M + H] + without radical cations and simultaneously analyzed using gas chromatography (GC)/electrospray ionization (ESI)-tandem mass spectrometry (MS/MS). The ionization profile, dissociation, and sensitivity were first investigated to understand the significant behavior of gas-phase PAHs under ESI. The formation of protonated molecular ions of PAHs was distinguished according to the analyte phase and ESI spray solvents. The protonated PAHs exhibited characteristic dissociations, such as H-loss, H 2 -loss, and acetylene-loss, via competition of internal energy. In addition, GC/ESI-MS/MS resulted in relatively lower concentration levels (better sensitivity) for the limits-of-detection (LODs) of PAHs than liquid chromatography (LC)/ESI-MS/MS, and it seems to result from the characteristic ionization mechanism of the gas-phase analyte under ESI. Furthermore, the LODs of gas-phase PAHs depended on molecular weight and proton affinity (PA). Consequently, we demonstrated the relationship among the analyte phases, sensitivities, and structural characteristics (molecular weight and PA) under ESI. The gas-phase PAHs provided enhanced protonation efficiency and sensitivity using GC/ESI-MS/MS, as their molecular weight and PA increased. Based on these results, we offered important information regarding the behavior of gas-phase analytes under ESI. Therefore, the present GC/ESI-MS/MS method has potential as an alternative method for simultaneous analysis of PAHs.

  16. Electron spectrometer for gas-phase spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

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

    International Nuclear Information System (INIS)

    Rutherford, W.M.


    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

  18. Catalytic combustion in gas stoves - Phase II

    Energy Technology Data Exchange (ETDEWEB)

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


    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

  19. Microfabricated Gas Phase Chemical Analysis Systems

    Energy Technology Data Exchange (ETDEWEB)



    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.

  20. Fluidized-Bed Silane-Decomposition Reactor (United States)

    Iya, Sridhar K.


    Fluidized-bed pyrolysis reactor produces high-purity polycrystalline silicon from silane or halosilane via efficient heterogeneous deposition of silicon on silicon seed particles. Formation of silicon dust via homogeneous decomposition of silane minimized, and deposition of silicon on wall of reactor effectively eliminated. Silicon used to construct solar cells and other semiconductor products.

  1. SVOC partitioning between the gas phase and settled dust indoors (United States)

    Weschler, Charles J.; Nazaroff, William W.


    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.

  2. Gas and particulate phase products from the ozonolysis of acenaphthylene (United States)

    Riva, Matthieu; Healy, Robert M.; Tomaz, Sophie; Flaud, Pierre-Marie; Perraudin, Emilie; Wenger, John C.; Villenave, Eric


    Polycyclic aromatic hydrocarbons (PAHs) are recognized as important secondary organic aerosol (SOA) precursors in the urban atmosphere. In this work, the gas-phase ozonolysis of acenaphthylene was investigated in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) for on-line characterization of the oxidation products in the gas and particle phases, respectively. SOA samples were also collected on filters and analyzed by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). The major gas-phase products included a range of oxygenated naphthalene derivatives such as 1,8-naphthalic anhydride, naphthalene 1,8-dicarbaldehyde and naphthaldehyde, as well as a secondary ozonide. Possible reaction mechanisms are proposed for the formation of these products and favoured pathways have been suggested. Many of these products were also found in the particle phase along with a range of oligomeric compounds. The same range of gas and particle phase products was observed in the presence and absence of excess cyclohexane, an OH scavenger, indicating that OH radical production from the ozonolysis of acenaphthylene is negligible. SOA yields in the range 23-37% were determined and indicate that acenaphthylene ozonolysis may contribute to part of the SOA observed in urban areas.

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

    DEFF Research Database (Denmark)

    Li, Bo; Sun, Zhiwei; Li, Zhongshan


    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...... homogeneous systems are required to characterize the gas-phase formation of alkali sulfates. We have measured the temperature and gas-phase concentrations of KCl and HCl, and detected the presence of aerosols in the post-flame region of a range of hydrocarbon flames seeded with KCl, with and without...... and HCl and aerosols formed, most pronounced in flames with the lowest post-flame temperatures. This shows that KCl is sulfated in the gas phase to K2SO4, and this is followed by homogeneous nucleation of K2SO4 to form aerosols. Predictions from a kinetic model of the S/Cl/K chemistry agreed well...

  4. Phase space analysis of some interacting Chaplygin gas models

    Energy Technology Data Exchange (ETDEWEB)

    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)


    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.)

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

    DEFF Research Database (Denmark)

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


    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...... 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...

  6. Reactive intermediates in the gas phase generation and monitoring

    CERN Document Server

    Setser, D W


    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

  7. Analytical study of solids-gas two phase flow

    International Nuclear Information System (INIS)

    Hosaka, Minoru


    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.)

  8. Anti-adhesive layers on stainless steel using thermally stable dipodal perfluoroalkyl silanes (United States)

    Kaynak, Baris; Alpan, Cüneyt; Kratzer, Markus; Ganser, Christian; Teichert, Christian; Kern, Wolfgang


    In this study steel surfaces are modified with dipodal perfluoroalkyl organosilanes and the resulting wetting properties and surface morphologies are analyzed. Dipodal silane monomers with different fluoroalkyl spacer lengths are synthesized via hydrosilylation reaction. The modification of stainless steel surfaces is performed in a two-step procedure comprising a corona activation of the steel surface and the subsequent reaction of surface hydroxyl groups with the dipodal silanes from the liquid phase. Anti-adhesive behavior on the surface is achieved through the modification. The attachment of the dipodal silanes on the stainless steel surface is validated with infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy. The wetting properties of the dipodal silane layers are investigated by contact angle measurements and adhesive force measurements. Atomic force microscopy is used to characterize the surface roughness and morphologies. Stainless steel modified with the dipodal perfluoroalkyl silanes exhibits low surface energy and low adhesive force compared to the unmodified steel surface. The thermal stability of coatings based on dipodal silanes is higher when compared to layers based on conventional monopodal organosilanes.

  9. Uncatalyzed thermal gas phase aziridination of alkenes by organic ...

    Indian Academy of Sciences (India)

    Alkene aziridination by azides through uncatalyzed thermal gas phase routes has been studiedusing the DFT B3LYP/6-31G(d,p) method, where the possible role of discrete nitrene intermediates is emphasized.The thermal decomposition of azides is studied using the MP2/aug-cc-pVDZ strategy as well. The MP2(but not the ...

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

    NARCIS (Netherlands)

    Pfeiffer, T.V.; Kedia, P.; Messing, M.E.; Valvo, M.; Schmidt-Ott, A.


    This article introduces a continuous, gas-phase method for depositing thin metallic coatings onto (nano)particles 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

  11. Nanoparticles-chemistry, new synthetic approaches, gas phase ...

    Indian Academy of Sciences (India)

    Abstract. In this paper, an overview of the synthesis, chemistry and applications of nanosystems carried out in our laboratory is presented. The discussion is divided into four sections, namely (a) chemistry of nanoparticles, (b) development of new synthetic approaches, (c) gas phase clusters and (d) device structures and ...

  12. Headspace solid-phase microextraction and gas chromatography ...

    African Journals Online (AJOL)

    Purpose: To extract and analyze the volatile components of Chrysanthemum morifolium Ramat. 'huaiju' by headspace solid-phase microextraction (HS-SPME) and gas chromatography–mass spectrometry. (GC–MS). Methods: Volatile components were extracted by HS-SPME and identified by GC–MS. The relative contents ...

  13. Nanoparticles-chemistry, new synthetic approaches, gas phase ...

    Indian Academy of Sciences (India)

    Home; Journals; Pramana – Journal of Physics; Volume 65; Issue 4. Nanoparticles-chemistry ... in our laboratory is presented. The discussion is divided into four sections, namely (a) chemistry of nanoparticles, (b) development of new synthetic approaches, (c) gas phase clusters and (d) device structures and applications.

  14. Gas phase and solution structures of 1-methoxyallenyllithium. (United States)

    Dixon, Darryl D; Tius, Marcus A; Pratt, Lawrence M


    A combined computational and (13)C NMR study was used to determine the solution structures of 1-methoxyallenyllithium. The gas phase calculations indicated that this species is aggregated as a hexamer. The NMR spectra in THF solution, together with the calculated aggregation energies and chemical shifts, are consistent with a dimer-tetramer equilibrium.

  15. Headspace solid-phase microextraction and gas chromatography ...

    African Journals Online (AJOL)

    Purpose: To extract and analyze the volatile components of Chrysanthemum morifolium Ramat. 'huaiju' by headspace solid-phase microextraction (HS-SPME) and gas chromatography–mass spectrometry (GC–MS). Methods: Volatile components were extracted by HS-SPME and identified by GC–MS. The relative contents ...

  16. Gas phase toluene isopropylation over high silica mordenite

    Indian Academy of Sciences (India)

    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 ...

  17. Gas-Phase IR Spectroscopy of Deprotonated Amino Acids

    NARCIS (Netherlands)

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


    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),

  18. Infrared spectroscopy of ionized corannulene in the gas phase

    NARCIS (Netherlands)

    Alvaro Galué, H.; Rice, C.A.; Steill, J.D.; Oomens, J.


    The gas-phase infrared spectra of radical cationic and protonated corannulene were recorded by infrared multiple-photon dissociation (IRMPD) spectroscopy using the IR free electron laser for infrared experiments. Electrospray ionization was used to generate protonated corannulene and an IRMPD

  19. Survey of the preparation, purity, and availability of silanes

    Energy Technology Data Exchange (ETDEWEB)

    Lorenz, J.H.


    Silane and disilane are currently available as prepared for the semiconductor market. Published or public information on preparative methods for monosilane and higher silanes are discussed. Purification techniques are reviewed. Data from current silane suppliers are tabulated. A short review of the silanes in Japan is given. Analytical procedures are not now perfected to determine group 3 or 5 elements in silane. All commercial silanes contain certain impurities. There is no simple one step purification technique for silane which a user could easily operate. Typical and actual analyses of commercial silane are given. Disilane is still in the development stage with only small quantities available at very high prices. The silane process developed in part under the DOE/JPL Flat Plate Solar Array project by Union Carbide is summarized. Higher purity silanes are now appearing on the market. These should be useful in the photovoltaic area.

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

    International Nuclear Information System (INIS)

    Strickert, R.G.


    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

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

    DEFF Research Database (Denmark)

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


    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...

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

    DEFF Research Database (Denmark)

    Haumann, Marco; Dentler, Katharina; Joni, Joni


    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...

  3. SILP catalysis in gas-phase hydroformylation and carbonylation

    Energy Technology Data Exchange (ETDEWEB)

    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


    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.)

  4. Poly(silyl silane) homo and copolymers (United States)

    Zeigler, J.K.


    Poly(silyl silanes) have been prepared. They have high photosensitivity and excellent resistance to oxygen-reactive ion etching processes. They are useful as photodepolymerizable photoresists, barrier layers, etc.

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

    DEFF Research Database (Denmark)

    Yang, Yan; Wang, Shuli; Wen, Chuang


    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...

  6. Harvesting Hydrogen Gas from Air Pollutants with an Unbiased Gas Phase Photoelectrochemical Cell. (United States)

    Verbruggen, Sammy W; Van Hal, Myrthe; Bosserez, Tom; Rongé, Jan; Hauchecorne, Birger; Martens, Johan A; Lenaerts, Silvia


    The concept of an all-gas-phase photoelectrochemical (PEC) cell producing hydrogen gas from volatile organic contaminated gas and light is presented. Without applying any external bias, organic contaminants are degraded and hydrogen gas is produced in separate electrode compartments. The system works most efficiently with organic pollutants in inert carrier gas. In the presence of oxygen, the cell performs less efficiently but still significant photocurrents are generated, showing the cell can be run on organic contaminated air. The purpose of this study is to demonstrate new application opportunities of PEC technology and to encourage further advancement toward PEC remediation of air pollution with the attractive feature of simultaneous energy recovery and pollution abatement. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    International Nuclear Information System (INIS)

    Munday, E.B.


    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

  8. Headgroup effect on silane structures at buried polymer/silane and polymer/polymer interfaces and their relations to adhesion. (United States)

    Zhang, Chi; Shephard, Nick E; Rhodes, Susan M; Chen, Zhan


    Sum frequency generation (SFG) vibrational spectroscopy was used to study the effect of silane headgroups on the molecular interactions that occur between poly(ethylene terephthalate) (PET) and various epoxy silanes at the PET/silane and PET/silicone interfaces. Three different silanes were investigated: (3-glycidoxypropyl) trimethoxysilane (γ-GPS), (3-glycidoxypropyl) methyl-dimethoxysilane (γ-GPMS), and (3-glycidoxypropyl) dimethyl-methoxysilane (γ-GPDMS). These silanes share the same backbone and epoxy end group but have different headgroups. SFG was used to examine the interfaces between PET and each of these silanes, as well as silanes mixed with methylvinylsiloxanol (MVS). We also examined the interfaces between PET and uncured or cured silicone with silanes or silane-MVS mixtures. Silanes with different headgroups were found to exhibit a variety of methoxy group interfacial segregation and ordering behaviors at various interfaces. The effect of MVS was also dependent upon silane headgroup choice, and the interfacial molecular structures of silane methoxy headgroups were found to differ at PET/silane and PET/silicone interfaces. Epoxy silanes have been widely used as adhesion promoters for polymer adhesives; therefore, the molecular structures probed using SFG were correlated to adhesion testing results to understand the molecular mechanisms of silicone-polymer adhesion. Our results demonstrated that silane methoxy headgroups play important roles in adhesion at the PET/silicone interfaces. The presence of MVS can change interfacial methoxy segregation and ordering, leading to different adhesion strengths. © 2012 American Chemical Society

  9. Gas-phase photocatalysis in μ-reactors

    DEFF Research Database (Denmark)

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


    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......-sensitivity reactors. We demonstrate that the system exhibits great versatility in terms of photocatalyst, illumination source and target reaction....

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

    Directory of Open Access Journals (Sweden)

    Antonio Pereira Nascimento Filho


    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.

  11. Two-phase dynamics of gas-heated steam generators

    International Nuclear Information System (INIS)

    Schittke, H.J.


    The dynamic behavior of a once-through steam generator plant operating in the secondary loop of a gas-cooled high-temperature reactor is considered. The mathematical model used for the description of the thermohydraulics of the problem comprises not only the dynamic behavior of the primary heating gas flow and the tube wall temperatures but especially the effects of pressure dynamics in the secondary fluid and the relevant two-phase flow phenomena: using an additional momentum balance equation for the dynamics of the slip velocity it is shown that the analytical computation of the slip velocity it is shown that the analytical computation of slip and two-phase pressure drop effects from the model equations is possible without the use of external correlations. Based on this mathematical model a generally applicable computer model is used to simulate the dynamic response of a given system

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

    NARCIS (Netherlands)

    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

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

    International Nuclear Information System (INIS)

    Leskovar, M.


    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)

  14. Theory of Gas Injection: Interaction of Phase Behavior and Flow (United States)

    Dindoruk, B.


    The theory of gas injection processes is a central element required to understand how components move and partition in the reservoir as one fluid is displacing another (i.e., gas is displacing oil). There is significant amount of work done in the area of interaction of phase-behavior and flow in multiphase flow conditions. We would like to present how the theory of gas injection is used in the industry to understand/design reservoir processes in various ways. The tools that are developed for the theory of gas injection originates from the fractional flow theory, as the first solution proposed by Buckley-Leveret in 1940's, for water displacing oil in porous media. After 1960's more and more complex/coupled equations were solved using the initial concept(s) developed by Buckley-Leverett, and then Welge et al. and others. However, the systematic use of the fractional flow theory for coupled set of equations that involves phase relationships (EOS) and phase appearance and disappearance was mainly due to the theory developed by Helfferich in early 80's (in petroleum literature) using method of characteristics primarily for gas injection process and later on by the systematic work done by Orr and his co-researchers during the last two decades. In this talk, we will present various cases that use and extend the theory developed by Helfferich and others (Orr et al., Lake et al. etc.). The review of various injection systems reveals that displacement in porous media has commonalities that can be represented with a unified theory for a class of problems originating from the theory of gas injection (which is in a way generalized Buckley-Leverett problem). The outcome of these solutions can be used for (and are not limited to): 1) Benchmark solutions for reservoir simulators (to quantify numerical dispersion, test numerical algorithms) 2) Streamline simulators 3) Design of laboratory experiments and their use (to invert the results) 4) Conceptual learning and to investigate

  15. Ab initio study of gas phase and water-assisted tautomerization of ...

    Indian Academy of Sciences (India)


    Ab initio study of gas phase and water-assisted tautomerization of maleimide and formamide. 623. Figure 4. Keto to enol conversion of (a) maleimide and (b) formamide in gas phase. (c) maleimide and (d) forma- mide with water.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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. Fundamental thermochemical properties of amino acids: gas-phase and aqueous acidities and gas-phase heats of formation. (United States)

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


    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.

  18. DSMC Convergence for Microscale Gas-Phase Heat Conduction (United States)

    Rader, D. J.; Gallis, M. A.; Torczynski, J. R.


    The convergence of Bird's Direct Simulation Monte Carlo (DSMC) method is investigated for gas-phase heat conduction at typical microscale conditions. A hard-sphere gas is confined between two fully accommodating walls of unequal temperature. Simulations are performed for small system and local Knudsen numbers, so continuum flow exists outside the Knudsen layers. The ratio of the DSMC thermal conductivity to the Chapman-Enskog value in the central region is determined for over 200 combinations of time step, cell size, and number of computational molecules per cell. In the limit of vanishing error, this ratio approaches 1.000 to within the correlation uncertainty. In the limit of infinite computational molecules per cell, the difference from unity depends quadratically on time step and cell size as these quantities become small. The coefficients of these quadratic terms are in good agreement with Green-Kubo values found by Hadjiconstantinou, Garcia, and co-workers. These results demonstrate that DSMC can accurately simulate microscale gas-phase heat conduction. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  19. Physical and mathematical modeling of one-dimensional and two-dimensional structures of detonation waves in a silane-air mixture (United States)

    Tropin, D. A.; Fedorov, A. V.; Fomin, P. A.


    The paper deals with the problem of the 1D and 2D structures of detonation waves (DW) in the silane-air mixture within the framework of mathematical model of a nonequilibrium gas dynamics. Detailed kinetics scheme of silane oxidation as well as the newly developed reduced kinetic model of detonation combustion of silane are used. On its basis the DW structure in stoichiometric silane - air mixture and dependences of Chapman-Jouguet parameters of mixture on stoichiometric ratio between the fuel (silane) and an oxidizer (air) were obtained. It was revealed that in the reaction zone, in the structure of DW, the heat release in the model with detailed kinetics is non-monotonic.

  20. Why does silane enhance the protective properties of epoxy films? (United States)

    Wang, Peng; Schaefer, Dale W


    Using neutron reflectivity, the protection mechanisms of a novel one-step epoxy-silane coating system were investigated in terms of coating structure and water response behavior. By comparing pure epoxy and epoxy-silane mixtures in various aqueous environments, the effects of the addition of silane were determined. Specifically, a bridged bis-silane coupling agent with six alkoxy moieties and a polysulfur bridge was investigated. The key mechanisms of silane-enhanced protection are (1) the silane is enriched at the substrate-coating interface, forming a hydrophobic dense interfacial layer and good adhesion to the substrate, and (2) the silane serves as a cross-linker, resulting in a denser and less hydrophilic bulk film compared to the neat epoxy. The hydrophobic nature of bis-sulfur silane also increases the overall hydrophobicity of the mixed film.

  1. Chemical modification of organoclay cloisite ®30B with silane 3-aminopropyltriethoxysilane

    International Nuclear Information System (INIS)

    Bertuoli, P.T.; Frizzo, V.P.; Zattera, A.J.; Scienza, L.C.


    The montmorillonite (MMT) is the inorganic phase more used in obtaining polymer nanocomposites. To improve the compatibility and dispersion of MMT in the polymer resin, many researchers have performed the process of functionalization of the clay with silane. This study was performed with the objective of modifying the Cloisite®30B clay with 3-aminopropyltriethoxysilane (APS). The modification was carried out by ion-exchange method using 10 g of clay Cloisite®30B (MMT-30B), 500 mL of hydroalcoholic solution (75/25 v/v) and 10 g of silane. The clay modified with silane (S-MMT 30B ) was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR). Through the XRD was observed an increase in the basal spacing d 001 of 1.82 to 2.2 nm. With the analysis of TGA was observed that S-MMT 30B showed greater weight loss than MMT-30B due to decomposition of the silane. The presence of band at 1562 cm-1 in the FTIR spectrum of S-MMT 30B confirmed the presence of silane in the structure of the modified clay. (author)

  2. Structural and Chemical Characterization of Silica Spheres before and after Modification by Silanization for Trypsin Immobilization

    Directory of Open Access Journals (Sweden)

    Eduardo F. Barbosa


    Full Text Available In the last decades, silica particles of a variety of sizes and shapes have been characterized and chemically modified for several applications, from chromatographic separation to dental supplies. The present study proposes the use of aminopropyl triethoxysilane (APTS silanized silica particles to immobilize the proteolytic enzyme trypsin for the development of a bioreactor. The major advantage of the process is that it enables the polypeptides hydrolysis interruption simply by removing the silica particles from the reaction bottle. Silanized silica surfaces showed significant morphological changes at micro- and nanoscale level. Chemical characterization showed changes in elemental composition, chemical environment, and thermal degradation. Their application as supports for trypsin immobilization showed high immobilization efficiency at reduced immobilization times, combined with more acidic conditions. Indirect immobilization quantification by reversed-phase ultrafast high performance liquid chromatography proved to be a suitable approach due to its high linearity and sensitivity. Immobilized trypsin activities on nonmodified and silanized silica showed promising features (e.g., selective hydrolysis for applications in proteins/peptides primary structure elucidation for proteomics. Silanized silica system produced some preferential targeting peptides, probably due to the hydrophobicity of the nanoenvironment conditioned by silanization.

  3. High purity silane and silicon production (United States)

    Breneman, William C. (Inventor)


    Silicon tetrachloride, hydrogen and metallurgical silicon are reacted at about C. and at pressures in excess of 100 psi, and specifically from about 300 up to about 600 psi to form di- and trichlorosilane that is subjected to disproportionation in the presence of an anion exchange resin to form high purity silane. By-product and unreacted materials are recycled, with metallurgical silicon and hydrogen being essentially the only consumed feed materials. The silane product may be further purified, as by means of activated carbon or cryogenic distillation, and decomposed in a fluid bed or free space reactor to form high purity polycrystalline silicon and by-product hydrogen which can be recycled for further use. The process results in simplified waste disposal operations and enhances the overall conversion of metallurgical grade silicon to silane and high purity silicon for solar cell and semiconductor silicon applications.

  4. Flammability limits of silane/perfluorocarbon/nitrogen mixtures


    Ohtani, Hideo


    Perfluorocarbons are known to react with silane because silane is a very strong reducing agent. However, quantitative information on their explosion limits are not known. So, in this study, flammability of silane/perfluorocarbon/nitrogen was examined experimentally. Their flammability areas were revealed quantitatively as triangular flammability diagrams, and the fact that perfluorocarbon reacts with silane was ascertained. (C) 2004 Elsevier Ltd.. All rights reserved.

  5. Unimolecular Gas-Phase Thermolysis of Ethyl Acetate

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Carlsen, Lars


    The unimolecular gas-phase thermolysis of ethyl acetate has been investigated by the Flash-Vacuum-Thermolysis/Field-Ionization Mass Spectrometry (FVT/FI-MS) method in combination with Collision Activation (CA) mass spectrometry at 1253K. Two predominant reactions are observed: elimination...... of ethylene affording acetic acid, the latter to some extent consecutively yielding ketene, and intramolecular oxygen to oxygen ethyl group migration. Additionally minor amounts of acetaldehyde is formed. The mechanistic aspects are discussed based on 18O and 18O/ 13C labelling....

  6. 40 CFR 721.9497 - Trifunctional ketoximino silane. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Trifunctional ketoximino silane. 721... Substances § 721.9497 Trifunctional ketoximino silane. (a) Chemical substance and significant new uses... silane (PMNs P-95-605 and P-95-606) are subject to reporting under this section for the significant new...

  7. 40 CFR 721.10053 - Alkyl silane methacrylate (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl silane...

  8. Production Decline Analysis for Two-Phase Flow in Multifractured Horizontal Well in Shale Gas Reservoirs


    Xie, Wei-Yang; Li, Xiao-Ping; Zhang, Lie-Hui; Tan, Xiao-Hua; Wang, Jun-Chao; Wang, Hai-Tao


    After multistage fracturing, the flowback of fracturing fluid will cause two-phase flow through hydraulic fractures in shale gas reservoirs. With the consideration of two-phase flow and desorbed gas transient diffusion in shale gas reservoirs, a two-phase transient flow model of multistage fractured horizontal well in shale gas reservoirs was created. Accurate solution to this flow model is obtained by the use of source function theory, Laplace transform, three-dimensional eigenvalue method, ...

  9. Polaronic exciton behavior in gas-phase water (United States)

    Udal'tsov, Alexander V.


    Features of the absorption spectrum of gas-phase water in the energy range 7-10 eV have been considered applying polaronic exciton theory. The interaction of the incident photon generating polaronic exciton in water is described taking into account angular momentum of the electron so that polaronic exciton radii have been estimated in dependence on spin-orbit coupling under proton sharing. The suggested approach admits an estimate of kinetic and rotation energies of the polaronic exciton. As a result sixteen steps of half Compton wavelength, λC/2 = h/(2mec) changing polaronic exciton radius were found consistent with local maxima and shoulders in the spectrum. Thus, the absorption of gas-phase water in the energy range 8.5-10 eV has been interpreted in terms of polaronic exciton rotation mainly coupled with the proton sharing. The incident photon interaction with water is also considered in terms of Compton interaction, when the rotation energy plays a role like the energy loss of the incident photon under Compton scattering. The found symmetry and the other evidence allowed to conclude about polaronic exciton migration under the interaction angle 90°.

  10. Closed-cage tungsten oxide clusters in the gas phase. (United States)

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


    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.

  11. Effect of the cross-linking silane concentration in a novel silane system on bonding resin-composite cement

    NARCIS (Netherlands)

    Matinlinna, Jukka; Ozcan, Mutlu; Lassila, Lippo; Kalk, Warner; Vallittu, Pekka


    Objective. Four experimental blends of an organo-functional silane monomer with a non-functional cross-linking silane monomer (a novel silane system) were evaluated as adhesion promoters in an experiment in which a resin-composite cement was bonded to silica-coated titanium. Material and Methods.

  12. Silane as an ignition aid in scramjets (United States)

    Morris, N. A.; Morgan, R. G.; Paull, A.; Stalker, R. J.


    This paper presents the results of experiments on silane/hydrogen combustion in a scramjet model configured as a constant area duct with a central injector. Intake flow conditions were created by free piston shock tunnels with simulated flight speeds ranging between 1.4 and 4.2 km/s. Intake conditions were restricted to three nominal Mach numbers. Boundary layer heating appeared to be responsible for ignition at low temperature, high Mach number conditions. Concentration of silane in hydrogen was varied, as well as intake temperature and pressure. Results indicated that silane in concentrations as low as 2.5 percent in hydrogen, was effective as a fuel additive for scramjets at conditions where hydrogen alone could not support combustion. An unsteady effect was observed as the intake temperature approached the lower limit for combustion. The combustion temperature limit rose significantly as the intake pressure was reduced to low levels. Computer simulations using a one dimensional premixed analysis suggested that although silane enhanced the combustion process, it was strongly dependent on the initial concentration of free radical oxygen. Results from the simulations were comparable to experimental results for some conditions.

  13. Partitioning of organic aerosol components between gas phase and particulate phase (United States)

    Folkers, M.; Mentel, T. F.; Henk, H.; Tillmann, R.; Wahner, A.; Otjes, R. P.; Blom, M. J.; ten Brink, H. M.


    To understand the role of organics in aerosols both the particulate composition and the gas/vapor phase composition must determined simultaneously. Ammonium sulfates and dicarboxylic acids are major components of continental, tropospheric aerosols. We performed two experiments in which we studied the partitioning of organic aerosol components between the gas and the particulate phase. As model systems we chose (NH4HSO_4 + glutaric acid) aerosol and ((NH4)HSO_4 + methyl glyoxal) aerosol (an oxidation product of isoprene). The experiment were performed in the large Aerosol Chamber at the FZ-Jülich at room temperature. The relative humidity was constantly increased in the course of the experiment (40 -> 90% r.h., 60 -> 90% r.h.).\

  14. Frequency metrology of a photomixing source for gas phase spectroscopy (United States)

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


    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.

  15. Visible and ultraviolet spectroscopy of gas phase protein ions. (United States)

    Antoine, Rodolphe; Dugourd, Philippe


    Optical spectroscopy has contributed enormously to our knowledge of the structure and dynamics of atoms and molecules and is now emerging as a cornerstone of the gas phase methods available for investigating biomolecular ions. This article focuses on the UV and visible spectroscopy of peptide and protein ions stored in ion traps, with emphasis placed on recent results obtained on protein polyanions, by electron photodetachment experiments. We show that among a large number of possible de-excitation pathways, the relaxation of biomolecular polyanions is mainly achieved by electron emission following photo-excitation in electronically excited states. Electron photodetachment is a fast process that occurs prior to relaxation on vibrational degrees of freedom. Electron photodetachment yield can then be used to record gas phase action spectra for systems as large as entire proteins, without the limitation of system size that would arise from energy redistribution on numerous modes and prevent fragmentation after the absorption of a photon. The optical activity of proteins in the near UV is directly related to the electronic structure and optical absorption of aromatic amino acids (Trp, Phe and Tyr). UV spectra for peptides and proteins containing neutral, deprotonated and radical aromatic amino acids were recorded. They displayed strong bathochromic shifts. In particular, the results outline the privileged role played by open shell ions in molecular spectroscopy which, in the case of biomolecules, is directly related to their reactivity and biological functions. The optical shifts observed are sufficient to provide unambiguous fingerprints of the electronic structure of chromophores without the requirement of theoretical calculations. They constitute benchmarks for calculating the absorption spectra of chromophores embedded in entire proteins and could be used in the future to study biochemical processes in the gas phase involving charge transfer in aromatic amino acids

  16. Silane surface modification for improved bioadhesion of esophageal stents (United States)

    Karakoy, Mert; Gultepe, Evin; Pandey, Shivendra; Khashab, Mouen A.; Gracias, David H.


    Stent migration occurs in 10-40% of patients who undergo placement of esophageal stents, with higher migration rates seen in those treated for benign esophageal disorders. This remains a major drawback of esophageal stent therapy. In this paper, we propose a new surface modification method to increase the adhesion between self-expandable metallic stents (SEMS) and tissue while preserving their removability. Taking advantage of the well-known affinity between epoxide and amine terminated silane coupling agents with amine and carboxyl groups that are abundant in proteins and related molecules in the human body; we modified the surfaces of silicone coated esophageal SEMS with these adhesive self-assembled monolayers (SAMs). We utilized vapor phase silanization to modify the surfaces of different substrates including PDMS strips and SEMS, and measured the force required to slide these substrates on a tissue piece. Our results suggest that surface modification of esophageal SEMS via covalent attachment of protein-binding coupling agents improves adhesion to tissue and could offer a solution to reduce SEMS migration while preserving their removability. PMID:25663731

  17. Gas-phase experiments on Au(III) photochemistry. (United States)

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


    Irradiation of AuCl(4)(-) and AuCl(2)(OH)(2)(-) in the gas-phase using ultraviolet light (220-415 nm) leads to their dissociation. Observed fragment ions for AuCl(4)(-) are AuCl(3)(-) and AuCl(2)(-) and for AuCl(2)(OH)(2)(-) are AuCl(2)(-) and AuClOH(-). All fragment channels correspond to photoreduction of the gold atom to either Au(II) or Au(I) depending on the number of neutral ligands lost. Fragment branching ratios of AuCl(4)(-) are observed to be highly energy dependent and can be explained by comparison of the experimental data to calculated threshold energies obtained using density functional theory. The main observed spectral features are attributed to ligand-to-metal charge transfer transitions. These results are discussed in the context of the molecular-level mechanisms of Au(III) photochemistry.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  19. Conformational Study of Taurine in the Gas Phase (United States)

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


    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.

  20. UV Action Spectroscopy of Gas-Phase Peptide Radicals. (United States)

    Nguyen, Huong T H; Shaffer, Christopher J; Pepin, Robert; Tureček, František


    UV photodissociation (UVPD) action spectroscopy is reported to provide a sensitive tool for the detection of radical sites in gas-phase peptide ions. UVPD action spectra of peptide cation radicals of the z-type generated by electron-transfer dissociation point to the presence of multiple structures formed as a result of spontaneous isomerizations by hydrogen atom migration. N-terminal Cα radicals are identified as the dominant components, but the content of isomers differing in the radical defect position in the backbone or side chain depends on the nature of the aromatic residue with phenylalanine being more prone to isomerization than tryptophan. These results illustrate that spontaneous hydrogen atom migrations can occur in peptide cation-radicals upon electron-transfer dissociation.

  1. Sugar Synthesis from a Gas-Phase Formose Reaction (United States)

    Jalbout, Abraham F.; Abrell, Leif; Adamowicz, Ludwik; Polt, Robin; Apponi, A. J.; Ziurys, L. M.


    Prebiotic possibilities for the synthesis of interstellar ribose through a protic variant of the formose reaction under gas-phase conditions were studied in the absence of any known catalyst. The ion-molecule reaction products, diose and triose, were sought by mass spectrometry, and relevant masses were observed. Ab initio calculations were used to evaluate protic formose mechanism possibilities. A bilateral theoretical and experimental effort yielded a physical model for glycoaldehyde generation whereby a hydronium cation can mediate formaldehyde dimerization followed by covalent bond formation leading to diose and water. These results advance the possibility that ion-molecule reactions between formaldehyde (CH2O) and H3O+ lead to formose reaction products and inform us about potential sugar formation processes in interstellar space.

  2. Radiation polymerization of tetrafluoroethylene in gas-phase

    International Nuclear Information System (INIS)

    Enslin, S.E.; Schnautz, N.G.; Van der Ende, E.


    The radiation polymerization of tetrafluoroethylene in gas-phase was studied over a temperature range of -80 to 200 degrees Celsius and an irradiation dose-rate of 0,30 to 10,8 kGy h sup(-1). The rate of polymerization was observed during the course of the polymerization process, to be a zero-order function of monomer pressure. However, the rate of polymerization was profoundly influenced by the initial monomer pressure, in this case exhibiting a 4,6-order dependence. The rate of polymerization was also observed to exhibit a 0,36-order dependence on radiation intensity. Both the rate of polymerization and the molecular mass of the product, polytetrafluoroethylene, reached maximum values over the temperature range of 90 to 150 degrees Celsius. The activation energy for the polymerization process was determined to be 8,7 kJ mol sup(-1) over the temperature range of -80 to 90 degrees Celsius

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

    DEFF Research Database (Denmark)

    Løj, Lusi Hindiyarti


    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...... between K-containing species and radical pool under combustion conditions has been improved. The available K/O/H/Cl chemistry has been updated by using both experimental work and detailed kinetic modeling. The experimental work was done by introducing gaseous KCl to CO oxidation system under reducing...... level, but the effect levels off at high concentrations. The experimental data were interpreted in terms of a detailed chemical kinetic model and used to update the K/O/H/Cl chemistry. The oxidation of SO2 to SO3 under combustion conditions has been suggested to be the rate limiting step in the gaseous...

  4. Technical Procedures Management in Gas-Phase Detoxification Laboratory

    International Nuclear Information System (INIS)

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


    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

  5. Multiphase flow and transport caused by spontaneous gas phase growth in the presence of dense non-aqueous phase liquid. (United States)

    Roy, James W; Smith, James E


    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.

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

    Directory of Open Access Journals (Sweden)

    Tobias V. Pfeiffer


    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.

  7. Compressorless Gas Storage and Regenerative Hydrogen Purification, Phase I (United States)

    National Aeronautics and Space Administration — Microwave regenerative sorption media gas storage/delivery techniques are proposed to address both compressed gas management and hydrogen purification requirements...

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

    DEFF Research Database (Denmark)

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


    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......, there is significant difference in the structures, with a substantial increase in hydrogen bonds and exposure of hydrophobic parts in the gas phase. The structure of the salt bridge in the gas phase is also much more stable than in the (experimental) solution structure....

  9. Production Decline Analysis for Two-Phase Flow in Multifractured Horizontal Well in Shale Gas Reservoirs

    Directory of Open Access Journals (Sweden)

    Wei-Yang Xie


    Full Text Available After multistage fracturing, the flowback of fracturing fluid will cause two-phase flow through hydraulic fractures in shale gas reservoirs. With the consideration of two-phase flow and desorbed gas transient diffusion in shale gas reservoirs, a two-phase transient flow model of multistage fractured horizontal well in shale gas reservoirs was created. Accurate solution to this flow model is obtained by the use of source function theory, Laplace transform, three-dimensional eigenvalue method, and orthogonal transformation. According to the model’s solution, the bilogarithmic type curves of the two-phase model are illustrated, and the production decline performance under the effects of hydraulic fractures and shale gas reservoir properties are discussed. The result obtained in this paper has important significance to understand pressure response characteristics and production decline law of two-phase flow in shale gas reservoirs. Moreover, it provides the theoretical basis for exploiting this reservoir efficiently.

  10. Gas-phase synthesis of semiconductor nanocrystals and its applications (United States)

    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

  11. One-bottle silane coupling agent containing 4-META. (United States)

    Kitahara, Nobuya; Itoh, Kazuo; Kusunoki, Mizuho; Oikawa, Misa; Miyazaki, Takashi


    The effectiveness of commercial and experimental silane coupling agents was evaluated by measuring their shear bond strengths to a ceramic disk. Experimental one-bottle silane coupling agents were prepared using 3-MPTS, 4-META, and resin monomers. The surfaces of two ceramic disks (IPS e-max, Ivoclar Vivadent AG, Schaan, Lichtenstein) were treated by a silane coupling agent to bond them to each other; this bonding was mediated by a commercial flowable resin composite (Clearfil Majesty LV, Kuraray, Tokyo, Japan). A commercial silane coupling agent (Clearfil Porcelain Bond Activator, Kuraray, Tokyo, Japan) modified by adding 4-META exhibited a significantly higher bond strength than the unmodified commercial one-bottle silane coupling agent. Among the tested materials, two experimental one-bottle silane coupling agents composed of 5% 4-META, 45% 3-MPTS, and 50% resin monomers exhibited statistically highest bond strengths.

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

    International Nuclear Information System (INIS)

    Li Xiaoyan; Kuang Bo; Zhou Guoliang; Xu Jijun


    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

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

    DEFF Research Database (Denmark)

    Carlsen, Lars; Egsgaard, Helge; Schaumann, Ernst


    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 ......-thiololactone (11) followed by loss of CO, minor amounts of the ketone (6), formed analogously, and the keten (7), as a result of simple sulphur extrusion.......), 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 (b) electrocyclic ring closure into the corresponding three-membered oxathiiran (10). The latter is dominant at lower temperatures, whereas higher thermolysis temperatures favour atomic oxygen extrusion. At further elevated temperatures additional concurrent primary reactions, i.e. extrusions of SO...

  14. Experimental Determination of Gas Phase Thermodynamic Properties of Bimolecular Complexes (United States)

    Hansen, Anne S.; Maroun, Zeina; Mackeprang, Kasper; Kjaergaard, Henrik G.


    Accurate determination of the atmospheric abundance of hydrogen bound bimolecular complexes is necessary, as hydrogen bonds are partly responsible for the formation and growth of aerosol particles. The abundance of a complex is related to the Gibbs free energy of complex formation (Δ G), which is often obtained from quantum chemical calculations that rely on calculated values of the enthalpy (Δ H) and entropy (Δ S) of complex formation. However, calculations of Δ H and in particular Δ S are associated with large uncertainties, and accurate experimental values are therefore crucial for theoretical benchmarking studies. Infrared measurements of gas phase hydrogen bound complexes were performed in the 300 to 373 K range, and lead to a purely experimental determination of Δ H using the van't Hoff equation. Equilibrium constants were determined by combining an experimental and calculated OH-stretching intensity, from which values of Δ G and hence Δ S could be determined. Thus we can determine Δ G, Δ H and Δ S for a bimolecular complex. We find that in the 300 to 373 K temperature range the determined Δ H and Δ S values are independent of temperature.

  15. Effect of elevated carrier-gas pressure on hydraulic characteristics of gas-solid particle two-phase flow

    International Nuclear Information System (INIS)

    Timoshenko, V.I.; Knyshenko, Y.V.; Kopysov, V.F.; Gromov, E.N.


    The effect of elevated gas pressure on the hydraulic resistance and critical velocity of a two-phase flow is studied on a pneumatic-transport bench. It is established that for each working-pressure level there exists a limiting solid-phase concentration, the exceeding of which causes an abrupt rise in hydraulic resistance. 16 refs., 3 figs

  16. Humidity dependence of adhesion for silane coated microcantilevers

    International Nuclear Information System (INIS)

    De Boer, Maarten P.; Mayer, Thomas M.; Carpick, Robert W.; Michalske, Terry A.; Srinivasan, U.; Maboudian, R.


    This study examines adhesion between silane-coated micromachined surfaces that are exposed to humid conditions. Our quantitative values for interfacial adhesion energies are determined from an in-situ optical measurement of deformations in partly-adhered cantilever beams. We coated micromachined cantilevers with either ODTS (C(sub 18)H(sub 37)SiCl(sub 3)) or FDTS (C(sub 8)F(sub 17)C(sub 2)H(sub 4)SiCl(sub 3)) with the objective of creating hydrophobic surfaces whose adhesion would be independent of humidity. In both cases, the adhesion energy is significantly lower than for uncoated, hydrophilic surfaces. For relative humidities (RH) less than 95% (ODTS) and 80% (FDTS) the adhesion energy was extremely low and constant. In fact, ODTS-coated beams exposed to saturated humidity conditions and long (48 hour) exposures showed only a factor of two increase in adhesion energy. Surprisingly, FDTS coated beams, which initially have a higher contact angle (115(degree)) with water than do ODTS coated beams (112(degree)), proved to be much more sensitive to humidity. The FDTS coated surfaces showed a factor of one hundred increase in adhesion energy after a seven hour exposure to 90% RH. Atomic force microscopy revealed agglomerated coating material after exposed to high RH, suggesting a redistribution of the monolayer film. This agglomeration was more prominent for FDTS than ODTS. These findings suggest a new mechanism for uptake of moisture under high humidity conditions. At high humidities, the silane coatings can reconfigure from a surface to a bulk phase leaving behind locally hydrophilic sites which increase the average measured adhesion energy. In order for the adhesion increase to be observed, a significant fraction of the monolayer must be converted from the surface to the bulk phase

  17. An algorithm for testing of gas distribution phases in the internal combustion engines

    Directory of Open Access Journals (Sweden)

    T. Nicu


    Full Text Available A method and algorithm for testing the gas distribution phases of internal combustion engines are proposed. This method allows a way of testing the gas distribution phases, based on direct and continuous measurements of pressure in cylinders and negative pressure in the intake manifold for using in the real time.

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

    International Nuclear Information System (INIS)

    Vonk, W.F.M.


    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.)

  19. Importance of the gas phase role to the prediction of energetic material behavior: An experimental study (United States)

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


    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.

  20. A numerical investigation into factors affecting gas and aqueous phase plumes in the subsurface (United States)

    Thomson, N. R.; Sykes, J. F.; Van Vliet, D.


    An investigation into the face and transport of volatile organic compounds (VOCs) in the subsurface requires the consideration of contaminant mass in both the aqueous and soil gas phases. As a result of water/gas phase partitioning, contaminated by partitioning from underlying ground water pollution. Conversely, soil gas can be contaminated by partitioning from underlying ground water VOC plumes. This soil gas and aqueous phase interaction has motivated the popularity of soil gas sampling technology as a method of characterizing ground water VOC contamination. A finite-element-based numerical model was developed to accurately simulate the interaction between the soil gas phase and the aqueous phase. This interaction is complicated since the saturation of the aqueous phase varies dramatically across the capillary fringe. The two-phase flow equations for gas and water are used to describe the flow regime, while the advective-dispersive transport of the VOC is considered in both phases. Dissolution and volatilization from a non-mobile non-aqueous phase liquid is included as a volatile organic contaminant source. A deforming mesh allows the model to accurately track the water table movement, and a Eularian-Lagrangian formulation is used to control some of the numerical difficulties associated with the numerical solution of the advection-dispersion equation. An investigation into diffusion of a VOC from below the water table demonstrated that both the frequency and the magnitude of water table fluctuations have a profound influence on the degree of soil gas contamination. Two-dimensional large-scale, long-term simulations were performed to estimate the aqueous and soil gas phase plumes resulting from an immobilized trichloroethylene residual located in the unsaturated zone. The simulation results indicate that these plumes are very sensitive to the vertical position of the contaminant source. In addition, it was determined that seasonal fluctuations in soil gas VOC

  1. Axial Dispersion and Back-mixing of Gas Phase in Pebble Bed Reactor

    Directory of Open Access Journals (Sweden)

    Rahman Al-Musafir


    Full Text Available Despite the worldwide attended of pebble bed reactors (PBRs, there is a lack of fundamental understanding of the complex flow pattern. In this work, the non-ideal flow behavior of the gas phase which is used for cooling has been investigated experimentally in a 0.3 m diameter pebble bed. The extent of mixing and dispersion of the gas phase has been qualified. The effect of gas velocity on the axial dispersion has been investigated with range from 0.05 to 0.6 m/s covering both the laminar and turbulent flow regimes. Glass bead particles of 1.2 cm diameter and 2.5 gm/cm3 which is randomly and closely packed have been used to mimic the pebbles. An advanced gas tracer technique was applied to measure the residence time distribution (RTD of gas phase using impulse tracer. The axial dispersion coefficients of gas phase in the studied pebble bed have been estimated using the axial dispersion model (ADM. It was found that the flow pattern of the gas phase deviates from plug flow depending on the superficial gas velocity. The results showed that the dispersion of the gas reduces as the gas velocity and Reynolds numbers increased.

  2. Gas-Phase Combustion Synthesis of Aluminum Nitride Powder (United States)

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


    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.

  3. Engineered Materials for Advanced Gas Turbine Engine, Phase I (United States)

    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. Functionalized TiO2nanoparticles by single-step hydrothermal synthesis: the role of the silane coupling agents. (United States)

    Dalod, Antoine R M; Henriksen, Lars; Grande, Tor; Einarsrud, Mari-Ann


    A simple, robust and versatile hydrothermal synthesis route to in situ functionalized TiO 2 nanoparticles was developed using titanium(IV) isopropoxide as Ti-precursor and selected silane coupling agents (3-aminopropyltriethoxysilane (APTES), 3-(2-aminoethylamino)propyldimethoxymethylsilane (AEAPS), and n -decyltriethoxysilane (DTES)). Spherical nanoparticles (ca. 9 nm) with narrow size distribution were obtained by using DTES or by synthesis performed without silane coupling agents. Rod-like nanoparticles along with 9 nm spherical nanoparticles were formed using aminosilane coupling agents because of a combination of oriented attachment of nanoparticles and specific adsorption of the aminosilane on crystallographic faces of anatase nanoparticles. The nanoparticles were functionalized in situ and became hydrophobic as silanes reacted to form covalent bonds on the surface of TiO 2 . The versatility of the aqueous synthesis route was demonstrated, and by selecting the type of silane coupling agent the surface properties of the TiO 2 nanoparticles could be tailored. This synthesis route has been further developed into a two-step synthesis to TiO 2 -SiO 2 core-shell nanoparticles. Combustion of the silane coupling agents up to 700 °C leads to the formation of a nanometric amorphous SiO 2 layer, preventing growth and phase transition of the in situ functionalized nanoparticles.

  5. Silane decorated metallic nanorods for hydrophobic applications

    International Nuclear Information System (INIS)

    Kannarpady, Ganesh K.; Sharma, Rajesh; Liu Bo; Trigwell, Steve; Ryerson, Charles; Biris, Alexandru S.


    A novel technique to modify a metallic surface for anti-icing applications is presented. An oblique angle deposition (OAD) technique has been used to fabricate metallic nanorods of Aluminum and Tungsten on a glass substrate. A conformal coating of a silane has been applied using a molecular vapor deposition technique. The resulting surface has shown a static contact angle of 134 deg. with the water droplet. SEM, AFM and XPS have been used to study the surface modification. This is a highly promising approach for anti-icing applications due to its scalability at a very low cost.

  6. Influence of silane agent in magnetic properties of the type MFe2O4 (M = Co e NiZn)

    International Nuclear Information System (INIS)

    Santos, P.T.A.; Araujo, P.M.A.G.; Costa, A.C.F.M.; Cornejo, D.R.


    This paper proposes to evaluate the influence of silane agent on the magnetic properties of ferrite is a MFe 2 O 4 (M = Co and NiZn). The ferrites were synthesized by combustion reaction, the surface modified with 3-aminopropyltrimethoxysilane agent silane (APTS) and characterized by XRD, FTIR, EDX and magnetic measurements. The results indicated that after modification of the surface of the spinel single phase was maintained. Surface modification was achieved with efficiency and Si-O confirmed by FTIR analysis. The surface modification kept the ferrimagnetic behavior of ferrites. (author)

  7. CO2 Capture from Flue Gas by Phase Transitional Absorption

    Energy Technology Data Exchange (ETDEWEB)

    Liang Hu


    A novel absorption process called Phase Transitional Absorption was invented. What is the Phase Transitional Absorption? Phase Transitional Absorption is a two or multi phase absorption system, CO{sub 2} rich phase and CO{sub 2} lean phase. During Absorption, CO{sub 2} is accumulated in CO{sub 2} rich phase. After separating the two phases, CO{sub 2} rich phase is forward to regeneration. After regeneration, the regenerated CO{sub 2} rich phase combines CO{sub 2} lean phase to form absorbent again to complete the cycle. The advantage for Phase Transitional Absorption is obvious, significantly saving on regeneration energy. Because CO{sub 2} lean phase was separated before regeneration, only CO{sub 2} rich phase was forward to regeneration. The absorption system we developed has the features of high absorption rate, high loading and working capacity, low corrosion, low regeneration heat, no toxic to environment, etc. The process evaluation shows that our process is able to save 80% energy cost by comparing with MEA process.

  8. Surface modification of cured cement pastes by silane coupling agents. (United States)

    Stewart, Andrew; Schlosser, Brett; Douglas, Elliot P


    X-ray photoelectron spectroscopy (XPS) and static contact angle measurements were used to study the interaction between silane coupling agents and cured cement paste. Three different silane coupling agents were investigated: aminopropyltriethoxy silane (APTES), 3-glycidyloxypropyltrimethoxy silane (GPTMS), and methoxy-terminated polydimethxyl siloxane (PDMS). These silanes have different end groups, so the change in surface energy after undergoing a successful reaction between the silane and hydroxyls on the surface of the cement paste was demonstrated by a change in contact angle. Relative to untreated samples, APTES samples decreased the contact angle, PDMS samples increased the contact angle, and GPTMS did not show a significant change in contact angle. Samples with a water-to-cement ratio (w/c) of 0.5 showed a larger change in contact angle than 0.4 w/c ratio samples, because of a greater number of hydroxyl groups at the surface. Deconvolution of the O 1s and Si 2p XPS peaks were performed to determine contributions from bridging and nonbridging atoms. An increase in bridging silicon and oxygen atoms relative to untreated samples indicated successful silane condensation and that a covalent bond was formed between the cement paste and silanes.

  9. Experimental study of three-phase gas-lift

    NARCIS (Netherlands)

    Descamps, M.N.


    The gas-lift technique is a gravity-based pumping technique used for recovering oil from a production well. Gas injected at the bottom of the production pipe reduces the gravity component of the pressure drop and thereby, stimulates the supply of oil from the reservoir. This results in an enhanced

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

    International Nuclear Information System (INIS)

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


    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

  11. Reactions of molecular dications in the gas phase

    International Nuclear Information System (INIS)

    Tafadar, Nurun Nabi


    This thesis presents the results from a series of experiments investigating the reactivity of gas phase molecular dications with neutral collision partners, at collision energies between 3 and 13 eV in the laboratory frame using a crossed-beam apparatus. The experiments involve measurement of product ion intensities, which are determined by means of time of flight mass spectrometry. The experimental methodology, together with relevant theory is described in the thesis. The relative intensities of product ions formed are a powerful probe of the reaction mechanism. Where appropriate, the reactions are examined for isotope effects by using the isotopic analogue of the neutral collision partner. Our investigation of the CF 3 2+ /Ar collision system shows neutral loss and electron transfer dominating the product ion yield. The variation of the neutral loss ion yield with collision energy provides a first estimate of the bond energy of the weak CF 2 2+ -F bond. Ab initio calculations indicate the ground state of CF 3 2+ adopts a C 2V equilibrium geometry. We further conclude that at least two electronic states of CF 3 2+ are present in the dication beam. Intramolecular isotope effects in the reactions of CO 2 2+ and CF 3 2+ with HD indicate the operation of an intramolecular isotope effect, favouring the formation of the deuterated products DCF 2 + and DCO + . However, for the CF 3 2+ /HD system our data reveals no isotope effect for the formation of HF + and the DF + within our experimental uncertainty. Statistical effects have been suggested as an alternative to the orientational model previously used to explain these effects. In our investigation of the CF 3 2+ /H 2 /D 2 and CO 2 2+ /H 2 /D 2 collision systems, experiments indicate that no intermolecular effects are in operation and the observed collision energy dependence is symptomatic of the absence of a barrier to reaction. In the CF 3 2+ /H 2 /D 2 system we observe the formation of the XF + product ion; a

  12. Influence of silane and heated silane on the bond strength of lithium disilicate ceramics - An in vitro study. (United States)

    Abduljabbar, Tariq; AlQahtani, Mohammed Ayedh; Jeaidi, Zaid Al; Vohra, Fahim


    To evaluate the effect of silane application and silane heat treatment on lithium-disilicate ceramic when bonded to composite resin. Twelve blocks of lithium-disilicate (LD) ceramic were fabricated and bonding surfaces were etched using 9.5% hydrofluoric acid (90 seconds). Three experimental groups resulted from the various surface treatment combinations, which included, no silane application (NS) (controls), silane application (S) and silane heat treatment (HS) (100°C for 5 minutesutes). Ceramic and composite resin blocks were bonded using an adhesive resin and light cured restorative composite as a luting agent, under standard conditions. A total of 90 specimen sticks (8 x 1mm²) were subjected to micro-tensile bond strength testing. The means of micro-tensile bond strength (µ-tbs) of the study groups were analyzed using t-test and ANOVA. The tested specimens were analyzed for mode of failure using scanning electron microscopy (SEM). The highest µ-tbs value (42.6 ±3.70 MPa) was achieved for LD ceramics with heat-dried silane. Both silane application and heat treatment of silane resulted in significant (psilane and its heat treatment showed significant improvement in bond strength of lithium disilicate ceramic when bonded to composite.

  13. Mobile Passive Optical Imager for Remote Gas Detection, Phase I (United States)

    National Aeronautics and Space Administration — Tunable filters based on electro-optic effect have shown great potential in detecting gas concentration through obtaining its absorption spectrum. In filter-based...

  14. Highly Efficient Electrochemical Cryogenic Purge Gas Recovery System, Phase I (United States)

    National Aeronautics and Space Administration — Ongoing rocket test operations at NASA Stennis Space Center (SSC) result in substantial quantities of hydrogen gas that is flared from the facility in addition to...

  15. Hot Gas TVC For Planetary Ascent Vehicle, Phase I (United States)

    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...

  16. Advanced On Board Inert Gas Generation System (OBBIGS), Phase II (United States)

    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...

  17. Advanced Gas Sensing Technology for Space Suits, Phase II (United States)

    National Aeronautics and Space Administration — The gas sensor in the PLSS of the ISS EMU will meet its projected life in 2020, and NASA is planning to replace it. At present, only high TRL devices based on...

  18. Compact Sensor for Isotope and Trace Gas Analysis, Phase II (United States)

    National Aeronautics and Space Administration — We propose to develop and demonstrate a new sensor platform for isotope and trace-gas analysis that is appropriate for future planetary missions. Among other...

  19. Compact, Robust, Low Power High Sensitivity Gas Sensor, Phase I (United States)

    National Aeronautics and Space Administration — Miniaturized gas sensors with high sensitivity that are compact, low power and low weight are needed to support for NASA's airborne science missions, particularly...

  20. Advanced On Board Inert Gas Generation System (OBBIGS), Phase I (United States)

    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...

  1. Two-stage coal liquefaction without gas-phase hydrogen (United States)

    Stephens, H.P.


    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.

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

    International Nuclear Information System (INIS)

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


    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. Miscibility improvement of LDPE/PVA blends by using silane-coupling agent

    Directory of Open Access Journals (Sweden)

    Zuhair Jabbar Abdul Ameer


    Full Text Available  Mixing two polymers usually results in an immiscible system, characterized by a coarse, easy to alter morphology, and poor adhesion between the phases. These blends have large size domains of dispersed phase and poor adhesion between them. Therefore, miscibility of polymer blend must be improved by using suitable additives such as compatibilizer. In this study 5% of silane 3-(trimethoxysilylpropyl methacrylate is used as compatibilizer to improve the miscibility and compatibility of LDPE/PVA blends. The samples were prepared by using a twin screw extruder. LDPE and PVA have been mixed with different weight proportion. Several tests were carried out to identify the compatibility and miscibility of the blends such as tensile properties, hardness, density, Fourier transforms infrared FTIR, digital microscope, scanning electron microscopy SEM and differential scanning calorimetry DSC. Result show that tensile strength, young modulus, elongation at break, density and hardness is increased with silane addition to the blends. SEM and digital microscope shows an improvement in the miscibility due to the better interaction between the two polymers as silane is added.

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

    CERN Document Server

    Skripov, Vladimir P; Schmelzer, Jurn W P


    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

  5. Enhanced Membrane System for Recovery of Water from Gas-Liquid Mixtures, Phase I (United States)

    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...

  6. Fluorescence resonance energy transfer of gas-phase ions under ultra high vacuum and ambient conditions. (United States)

    Frankevich, Vladimir; Chagovets, Vitaliy; Widjaja, Fanny; Barylyuk, Konstantin; Yang, Zhiyi; Zenobi, Renato


    We report evidence for fluorescence resonance energy transfer (FRET) of gas-phase ions under ultra high vacuum conditions (10(-9) mbar) inside a mass spectrometer as well as under ambient conditions inside an electrospray plume. Two different FRET pairs based on carboxyrhodamine 6G (donor) and ATTO590 or Bodipy TR (acceptor) dyes were examined and their gas-phase optical properties were studied. Our measurements indicate a different behavior for the two FRET pairs, which can be attributed to their different conformations in the gas phase. Upon desolvation via electrospray ionization, one of the FRET pairs undergoes a conformational change that leads to disappearance of FRET. This study shows the promise of FRET to obtain a direct correlation between solution and gas-phase structures.

  7. Mobile Greenhouse Gas Flux Analyzer for Unmanned Aerial Vehicles, Phase I (United States)

    National Aeronautics and Space Administration — In this SBIR Phase I effort, Los Gatos Research (LGR) proposes to develop a highly-accurate, lightweight, low-power gas analyzer for eddy flux covariance...

  8. Mononuclear metavanadate catalyses gas phase oxidation of methanol to formaldehyde employing dioxygen as the terminal oxidant. (United States)

    Waters, Tom; Khairallah, George N; Wimala, Samantha A S Y; Ang, Yien C; O'Hair, Richard A J; Wedd, Anthony G


    Multistage mass spectrometry experiments reveal a sequence of gas phase reactions for the oxidation of methanol to formaldehyde with a mononuclear oxo vanadate anion as the catalyst and dioxygen as the terminal oxidant.

  9. Gas-Kinetic Computational Algorithms for Hypersonic Flows in Continuum and Transitional Regimes, Phase I (United States)

    National Aeronautics and Space Administration — This SBIR Phase I project explores two gas-kinetic computational algorithms for simulation of hypersonic flows in both continuum and transitional regimes. One is the...

  10. Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol (United States)

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


    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

  11. Separation of Flue Gas Components by SILP (Supported Ionic Liquid-Phase) Absorbers

    DEFF Research Database (Denmark)

    Thomassen, P.; Kunov-Kruse, Andreas Jonas; Mossin, Susanne L.


    . The results show that CO2, NO and SO2 can be reversible and selective absorbed using different ILs and that Supported Ionic Liquid-Phase (SILP) absorbers are promising materials for industrial flue gas cleaning. Absorption/desorption dynamics can be tuned by temperature, pressure and gas concentration. © 2012......Reversible absorption of the flue gas components CO2, NO, NO2 and SO2 has been tested for different ionic liquids (ILs) at different temperatures and flue gas compositions where porous, high surface area carriers have been applied as supports for the ionic liquids to obtain Supported Ionic Liquid......-Phase (SILP) absorber materials. The use of solid SILP absorbers with selected ILs were found to significantly improve the absorption capacity and sorption dynamics at low flue gas concentration, thus making the applicability of ILs viable in technical, continuous flow processes for flue gas cleaning...

  12. Determination of gas phase triacetone triperoxide with aspiration ion mobility spectrometry and gas chromatography-mass spectrometry. (United States)

    Räsänen, Riikka-Marjaana; Nousiainen, Marjaana; Peräkorpi, Kaleva; Sillanpää, Mika; Polari, Lauri; Anttalainen, Osmo; Utriainen, Mikko


    Aspiration ion mobility spectrometry (IMS) has been used for the first time to screen 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxacyclononane explosive, the most commonly known as triacetone triperoxide (TATP). Gaseous TATP was generated from synthesized solid compound, sublimed and directed to a portable chemical detection system comprised of an aspiration-type IMS detector and six semiconductor sensors. Different unknown TATP gas phase concentrations were produced and corresponding IMS and semiconductor responses were measured. The experimental concentrations were determined by gas chromatography-mass spectrometry (GC-MS). The results evidenced that the monitored compound in the gas phase was TATP. In addition, the determined TATP concentrations and corresponding IMS intensities showed that the IMS response values were proportional to the measured TATP concentrations.

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

    International Nuclear Information System (INIS)

    Joergensen, S.I.


    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.)

  14. Defect formation in fluoropolymer films at their condensation from a gas phase (United States)

    Luchnikov, P. A.


    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.

  15. Gas phase ion chemistry of coumarins: ab initio calculations used to ...

    African Journals Online (AJOL)

    The gas phase ion chemistry of coumarins using electron ionization (EI), positive chemical ionization (PCI) and negative chemical ionization (NCI) in a time of flight and quadrupole mass spectrometer (qMS) coupled to a gas chromatograph is outlined. The observations in NCI mode were complimented with Ab initio ...

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

    NARCIS (Netherlands)

    Malekzadeh, R.


    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

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

    NARCIS (Netherlands)

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


    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

  18. Optical pyrometer based on the gas phase photoacoustic effect. (United States)

    Meng, Xiangling; Diebold, Gerald J


    A photoacoustic cell containing an infrared active gas and equipped with a pair of infrared transmitting windows that alternately views two bodies at different temperatures through a pair of chopping wheels acts as a differential detector of the radiation emitted by the two bodies. A theory for the photoacoustic signal shows that the device acts to monitor the difference in the incidances between the two bodies integrated over the absorptions of the gas in the cell. Experiments are reported showing that the response of the pyrometer depends on the relative temperatures of heated bodies, the absorption coefficient of the gas in the cell, and the modulation frequency of the chopping wheels. The instrument is shown to be a sensitive detector of a null in the integrated incidance of the two bodies.

  19. Propagation characteristics of pulverized coal and gas two-phase flow during an outburst. (United States)

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


    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.

  20. Propagation characteristics of pulverized coal and gas two-phase flow during an outburst (United States)

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


    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. PMID:28727738

  1. Evaluation of silanes in SBR 1502 / Telinne Monspessulana flour composites

    Directory of Open Access Journals (Sweden)

    Oscar Buitrago

    Full Text Available Abstract A comparative study was performed on the effect of the addition of silane coupling agents (SCA, vinyltrimethoxysilane (VTMS and 3-aminopropyltriethoxysilane (APTES to a mixture of styrene butadiene rubber SBR1502 with Telinne Monspessulana flour (TMF. SCA was directly added into the mixture using untreated and mercerized TMF. Also, TMF and SBR1502 mixing trials were conducted with the TMF previously mercerized and injected with each of the silanes. The rubber compounds were subjected to tensile tests in order to evaluate the coupling power of both SCA. It was found that the vinyl silane type produced the best results in the tensile strength.

  2. Oriented xenon hydride molecules in the gas phase

    Czech Academy of Sciences Publication Activity Database

    Buck, U.; Fárník, Michal


    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

  3. Gas phase dispersion in a small rotary kiln

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, B.B.


    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/sup 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.

  4. Experimental and CFD investigation of gas phase freeboard combustion

    DEFF Research Database (Denmark)

    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...

  5. Gas phase dispersion in a small rotary kiln

    International Nuclear Information System (INIS)

    Spencer, B.B.


    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

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

    Energy Technology Data Exchange (ETDEWEB)



    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.

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

    International Nuclear Information System (INIS)

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


    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)

  8. Industrial fuel gas demonstration plant program. Current working estimate. Phase III and III

    Energy Technology Data Exchange (ETDEWEB)


    The United States Department of Energy (DOE) executed a contract with Memphis Light, Gas and Water Division (MLGW) which requires MLGW to perform process analysis, design, procurement, construction, testing, operation, and evaluation of a plant which will demonstrate the feasibility of converting high sulfur bituminous coal to industrial fuel gas with a heating value of 300 +- 30 Btu per standard cubic foot (SCF). The demonstration plant is based on the U-Gas process, and its product gas is to be used in commercial applications in Memphis, Tenn. The contract specifies that the work is to be conducted in three phases. The Phases are: Phase I - Program Development and Conceptual Design; Phase II - Demonstration Plant Final Design, Procurement and Construction; and Phase III - Demonstration Plant Operation. Under Task III of Phase I, a Cost Estimate for the Demonstration Plant was completed as well as estimates for other Phase II and III work. The output of this Estimate is presented in this volume. This Current Working Estimate for Phases II and III is based on the Process and Mechanical Designs presented in the Task II report (second issue) and the 12 volumes of the Task III report. In addition, the capital cost estimate summarized in the appendix has been used in the Economic Analysis (Task III) Report.

  9. Artificial Neural Network Modeling of Liquid Thermal Conductivity for alkanes, ketones and silanes (United States)

    Latini, G.; Di Nicola, G.; Pierantozzi, M.; Coccia, G.; Tomassetti, S.


    The values of thermal conductivity λ at different temperatures for organic and inorganic compounds in the liquid phase is essential in the study of numerous processes, but experimental data are frequently not available with acceptable reliability or not available at all, since rigorous theoretical or semi-theoretical models of the liquid state are usually of poor practical use for engineering purposes. The Artificial Neural Network (ANN) approach is a very powerful tool and it can be a good indicator of the lowest limit achievable with a selected database and with a selected set of inputs. This study investigates the applicability of the ANN as an efficient tool for the prediction of pure organic compounds’ thermal conductivity of three important families such as alkanes, ketones and silanes, for a wide range of temperatures. The families of n-alkanes, ketones and silanes were chosen to verify the general reliability of the proposed method when used in large temperature ranges for very different organic families, above all the silanes (compounds containing silicon), whose liquid thermal conductivity is experimentally investigated in very few cases. This method appears to be successful: in all reduced temperature range, along or near the saturation line, the average absolute deviations between calculated and experimental thermal conductivity data are 0.19% and the maximum absolute ones 2.44%

  10. Gas distribution equipment in hydrogen service - Phase II (United States)

    Jasionowski, W. J.; Huang, H. D.


    The hydrogen permeability of three different types of commercially available natural gas polyethylene pipes was determined. Ring tensile tests were conducted on permeability-exposed and as-received samples. Hydrogen-methane leakage experiments were also performed. The results show no selective leakage of hydrogen via Poiseuille, turbulent, or orifice flow (through leaks) on the distribution of blends of hydrogen and methane. The data collected show that the polyethylene pipe is 4 to 6 times more permeable to hydrogen than to methane.

  11. A gas-phase source term for Yucca Mountain

    International Nuclear Information System (INIS)

    Zwahlen, E.D.; Lee, W.W.L.; Pigford, T.H.; Chambre, P.L.


    We previously presented analyses of gas flow into and out of a partly failed nuclear waste container for various assumed hole sizes and failure times. We also estimated the release rate of 14 C by advection and counter-diffusion from the failed container. Here we present an estimate of 14 C release rate and cumulative release for hole sizes of one to 300-μm and failure at emplacement and 300 years. 4 refs., 4 figs

  12. Multiscale and luminescent, hollow microspheres for gas phase thermometry


    Bischoff, Lothar; Stephan, Michael; Birkel, Christina S.; Litterscheid, Christian F.; Dreizler, Andreas; Albert, Barbara


    Recently developed laser-based measurement techniques are used to image the temperatures and velocities in gas flows. They require new phosphor materials with an unprecedented combination of properties. A novel synthesis procedure is described here; it results in hierarchically structured, hollow microspheres of Eu3+-doped Y2O3, with unusual particle sizes and very good characteristics compared to full particles. Solution-based precipitation on polymer microballoons produces very stable and l...

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

    International Nuclear Information System (INIS)

    Chen, C.; Thomas, D.M.


    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

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

    International Nuclear Information System (INIS)

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


    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

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

    International Nuclear Information System (INIS)

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


    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

  16. The electron spectrum of UF6 recorded in the gas phase (United States)

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


    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.

  17. Nanoparticle coating on the silane-modified surface of magnesium for local drug delivery and controlled corrosion. (United States)

    Lee, Won Seok; Park, Min; Kim, Myung Hun; Park, Chun Gwon; Huh, Beom Kang; Seok, Hyun Kwang; Choy, Young Bin


    In this study, we proposed a potential method for the preparation of a magnesium-based medical device for local drug delivery and controlled corrosion. A magnesium surface was modified with 3-aminopropyltrimethoxy silane, and the resulting surface was then coated with drug-loaded nanoparticles made of poly (lactic-co-glycolic acid) via electrophoretic deposition. The drug-loaded nanoparticles (i.e., Tr_NP) exhibited a size of 250 ± 67 nm and a negative zeta potential of -20.9 ± 2.75 mV. The drug was released from the nanoparticles in a sustained manner for 21 days, and this did not change after their coating on the silane-modified magnesium. The silane-modified surface suppressed magnesium corrosion. When immersed in phosphate buffered saline at pH 7.4, the average rate of hydrogen gas generation was 0.41-0.45 ml/cm(2)/day, compared to 0.58-0.6 ml/cm(2)/day from a bare magnesium surface. This corrosion profile was not significantly changed after nanoparticle coating under the conditions employed in this work. The in vitro cell test revealed that the drug released from the coating was effective during the whole release period of 21 days, and both the silane-modified surface and carrier nanoparticles herein were not cytotoxic. © The Author(s) 2015.

  18. Magnesium silicide production and silane synthesis on its basis

    International Nuclear Information System (INIS)

    Taurbaev, T.I.; Mukashev, F.A.; Manakov, S.M.; Francev, U.V.; Kalblanbekov, B.M.; Akhter, P.; Abbas, M.; Hussain, A.


    We had developed an alternative method of production of magnesium silicide with use of ferroalloys of silicon. Magnesium silicide is raw material for silane synthesis. The essence of the method consist of sintering FS -75 (ferrosilicium with 75 % of silicon and 25 % of iron, made by ferroalloy factories) with metal magnesium at temperature of 650 deg. C. The X-ray analysis has shown formation of magnesium silicide. That is further used for synthesis of silane. The output of silane is 60 % in respect of the contents of silicon. After removing the water vapors the mass-spectrometer analysis has estimated the purity of silane as 99.95 % with no detection of phosphine and diborane. (author)

  19. Silane coupling agent for enhanced epoxy-iron oxide nanocomposite

    Directory of Open Access Journals (Sweden)

    Hamdy M. Naguib


    Full Text Available In this study, silane-treated Fe2O3 nanoparticles were successfully prepared using (3-aminopropyl triethoxysilane (APTES. The chemical structure and morphology of the obtained nanoparticles were investigated by several analysis techniques including FTIR, XRD, TEM and DLS. Both of untreated Fe2O3 (IO and silane-treated Fe2O3 (SIO nanoparticles were used in the preparation of epoxy nanocomposites with 5% by weight fraction. FTIR and XRD approved that SIO was successfully prepared with highly crystalline structure. TEM and DLS indicated the good dispersion of treated nanoparticles in the nanocomposite matrix, also the average particle size of nanofiller decreased to ∼200 nm after silane treatment. The dynamic properties for the prepared nanocomposites were studied using DMA and confirmed by nanoindentation technique. The results indicated that silane-treated nanoparticles can improve the hardness and Tg by 87.5% and 5 °C respectively at 5% weight fraction.

  20. Combined Silane Pyrolysis and Silicon-Particle Melt (United States)

    Levin, H.


    Melter directly coupled to pyrolyzer eliminates difficulties of transport. Proposed coupling of free-space silane pyrolyzer and melter without intervening steps produce molten silicon with no problems of fine-particle movement, storage, contamination in transport, or oxide formation.

  1. Poly(silyl silane)homo and copolymers (United States)

    Zeigler, John M.


    Poly(silyl silanes) have been prepared. They have high photosensitivity and excellent resistance to oxygen-reactive ion etching processes. They are useful as photodepolymerizable photoresists, barrier layers, etc.

  2. Lanthanum Tricyanide-Catalyzed Acyl Silane-Ketone Benzoin Additions (United States)

    Tarr, James C.; Johnson, Jeffrey S.


    Lanthanum tricyanide efficiently catalyzes a benzoin-type coupling between acyl silanes and ketones. Yields range from moderate to excellent over a broad substrate scope encompassing aryl, alkyl, electron-rich, and sterically hindered ketones. PMID:19655731

  3. Characterizing the correlations between local phase fractions of gas-liquid two-phase flow with wire-mesh sensor. (United States)

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


    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).

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

    International Nuclear Information System (INIS)

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


    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)

  5. Silanization of glass chips—A factorial approach for optimization (United States)

    Vistas, Cláudia R.; Águas, Ana C. P.; Ferreira, Guilherme N. M.


    Silanization of glass chips with 3-mercaptopropyltrimethoxysilane (MPTS) was investigated and optimized to generate a high-quality layer with well-oriented thiol groups. A full factorial design was used to evaluate the influence of silane concentration and reaction time. The stabilization of the silane monolayer by thermal curing was also investigated, and a disulfide reduction step was included to fully regenerate the thiol-modified surface function. Fluorescence analysis and water contact angle measurements were used to quantitatively assess the chemical modifications, wettability and quality of modified chip surfaces throughout the silanization, curing and reduction steps. The factorial design enables a systematic approach for the optimization of glass chips silanization process. The optimal conditions for the silanization were incubation of the chips in a 2.5% MPTS solution for 2 h, followed by a curing process at 110 °C for 2 h and a reduction step with 10 mM dithiothreitol for 30 min at 37 °C. For these conditions the surface density of functional thiol groups was 4.9 × 1013 molecules/cm2, which is similar to the expected maximum coverage obtained from the theoretical estimations based on projected molecular area (∼5 × 1013 molecules/cm2).

  6. Amphiphilic Silane Modified Multifunctional Nanoparticles for Magnetically Targeted Photodynamic Therapy. (United States)

    Sun, Xueke; Dong, Biao; Xu, Hongwei; Xu, Shihan; Zhang, Xinran; Lin, Yanxia; Xu, Lin; Bai, Xue; Zhang, Shuang; Song, Hongwei


    Efficient targeting is a major challenge in practical photodynamic therapy (PDT). Though the "enhanced permeability and retention" (EPR) effect is a widely used tumor targeting method, magnetic targeting strategy is more promising considering the issue of high targeting efficiency and reducing concentration-dependent toxicity. Herein, magnetic targeting and highly effective Fe 3 O 4 @Ce6/C6@silane NPs are reported as a class of precisely controlled photosensitizers (PS) for PDT. On the basis of the amphiphilic silane encapsulation, PS chlorin e6 (Ce6) and Coumarin 6 (C6) as well as Fe 3 O 4 NPs were coloaded into the inside hydrophobic environment of amphiphilic silane, forming a theranostic agent for dual-mode imaging guided and magnetic targeting enhanced in vivo PDT agent. To solve the problem of over-irradiation, the coloaded design of C6 and Ce6 molecules can afford the real time PDT monitoring by ratio emissions with same excitation wavelength. When Fe 3 O 4 @Ce6/C6@silane and Ce6/C6@silane NPs are compared in in vitro and in vivo experiments, the introduction of Fe 3 O 4 in the composite does not affect the PDT efficiency, whereas, in contrast, it brings MRI imaging and magnetic targeting functions. Fe 3 O 4 @Ce6/C6@silane injection followed with magnetic field (MF) and light irradiation is important in generating an effective PDT process, showing great potential in tumor therapy.

  7. Ethylene epoxidation promoted by methane gas-phase thermic oxidation. The influence of equivalence ratio and gas flow velocity

    International Nuclear Information System (INIS)

    Grigoryan, R.R.; Arsentiev, S.D.; Mantashyan, A.A.


    Ethylene epoxidation promoted by methane gas-phase thermic oxidation has been studied. The studies were carried out in a two-sectional reactor under flow conditions. The most experiments were performed at temperatures T 1 - 983 K, T 2 - 778 K and pressure P = 86,7 kPa. It was shown that when methane is oxidized in the first section of the reactor and ethylene is put into the second section, epoxidation of olefin occurs through the alkyl peroxy radical interaction with double bond of olefin. It was established that the dependences of epoxidation rate on equivalence ratio and gas flow velocity pass through maximum. The substitution of methane by inert gas (argon) in the first section leads to significant decrease of rate of ethylene oxide accumulation in the second section

  8. Cold flame on Biofilm - Transport of Plasma Chemistry from Gas to Liquid Phase (United States)

    Kong, Michael


    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

  9. Gas-phase kinetics modifies the CCN activity of a biogenic SOA. (United States)

    Vizenor, A E; Asa-Awuku, A A


    Our current knowledge of cloud condensation nuclei (CCN) activity and the hygroscopicity of secondary organic aerosol (SOA) depends on the particle size and composition, explicitly, the thermodynamic properties of the aerosol solute and subsequent interactions with water. Here, we examine the CCN activation of 3 SOA systems (2 biogenic single precursor and 1 mixed precursor SOA system) in relation to gas-phase decay. Specifically, the relationship between time, gas-phase precursor decay and CCN activity of 100 nm SOA is studied. The studied SOA systems exhibit a time-dependent growth of CCN activity at an instrument supersaturation of ∼0.2%. As such, we define a critical activation time, t 50 , above which a 100 nm SOA particle will activate. The critical activation time for isoprene, longifolene and a mixture of the two precursor SOA is 2.01 hours, 2.53 hours and 3.17 hours, respectively. The activation times are then predicted with gas-phase kinetic data inferred from measurements of precursor decay. The gas-phase prediction of t 50 agrees well with CCN measured t 50 (within 0.05 hours of the actual critical times) and suggests that the gas-to-particle phase partitioning may be more significant for SOA CCN prediction than previously thought.

  10. In Situ Environmental TEM in Imaging Gas and Liquid Phase Chemical Reactions for Materials Research. (United States)

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


    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.

  11. Modelling gas migration in compacted bentonite: gambit club phase 3. Final report

    International Nuclear Information System (INIS)

    Hoch, A.R.; Cliffe, K.A.; Swift, B.T.; Rodwell, W.R.


    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.)

  12. Contributions of gas-phase plasma chemistry to surface modifications and gas-surface interactions: investigations of fluorocarbon rf plasmas (United States)

    Cuddy, Michael F., II

    The fundamental aspects of inductively coupled fluorocarbon (FC) plasma chemistry were examined, with special emphasis on the contributions of gas-phase species to surface modifications. Characterization of the gas-phase constituents of single-source CF4-, C2F6-, C3F 8-, and C3F6-based plasmas was performed using spectroscopic and mass spectrometric techniques. The effects of varying plasma parameters, including applied rf power (P) and system pressure (p) were examined. Optical emission spectroscopy (OES) and laser-induced fluorescence (LIF) spectroscopy were employed to monitor the behavior of excited and ground CFx (x = 1,2) radicals, respectively. Mass spectrometric techniques, including ion energy analyses, elucidated behaviors of nascent ions in the FC plasmas. These gas-phase data were correlated with the net effect of substrate processing for Si and ZrO2 surfaces. Surface-specific analyses were performed for post-processed substrates via x-ray photoelectron spectroscopy (XPS) and contact angle goniometry. Generally, precursors with lower F/C ratios tended to deposit robust FC films of high surface energy. Precursors of higher F/C ratio, such as CF4, were associated with etching or removal of material from surfaces. Nonetheless, a net balance between deposition of FC moieties and etching of material exists for each plasma system. The imaging of radicals interacting with surfaces (IRIS) technique provided insight into the phenomena occurring at the interface of the plasma gas-phase and substrate of interest. IRIS results demonstrate that CFx radicals scatter copiously, with surface scatter coefficients, S, generally greater than unity under most experimental conditions. Such considerable S values imply surface-mediated production of the CFx radicals at FC-passivated sites. It is inferred that the primary route to surface production of CFx arises from energetic ion bombardment and ablation of surface FC films. Other factors which may influence the observed CFx

  13. Experimental and numerical investigation of gas phase freeboard combustion

    DEFF Research Database (Denmark)

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


    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...... approach with the De Soete global scheme and the combination of a skeletal combustion mechanism with the analytically reduced N scheme provided it reasonable agreement with the experimental data. Most of the tested ammonia oxidation schemes were able to qualitatively predict the trends in NO formation...... going from one operational case to the other, but the main combustion solution on which the ammonia oxidation was based proved to have a large impact on the quantitative NO prediction....

  14. Gas-phase chemistry of element 114, flerovium

    Directory of Open Access Journals (Sweden)

    Yakushev Alexander


    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.

  15. Corrosion protection of aluminum by silane-based surface treatment (United States)

    Song, Jun

    The possibility of using silane coupling agents as replacements for chromate treatments was investigated for aluminum substrates. In order to understand the influence of deposition parameters on silane film formation, pure Al substrates were used to study the interaction between silane coupling agents and aluminum surfaces. The silane films formed on pure A1 substrates from aqueous solutions were characterized by ellipsometry, contact angle measurements, reflection absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and Time-of Flight Secondary Ion Mass Spectrometry. The deposition parameters studied include solution concentration, solution dipping time and pH value of the applied solution. It appears that silane film formation involved a true equilibrium of hydrolysis and condensation in aqueous solution. It has been found that the silane film thickness obtained depends primarily on the solution concentration and is independent of the solution dipping time. The molecular orientation of the applied silane film is determined by the pH value of the applied silane solution and the isoelectic point of the metal substrates. The deposition window in terms of pH value for A1 substrates is between 4 and 7. The total surface energy of silane-coated A1 substrate decreases with film aging time, the decreased rate, however, is determined by the nature of silane coupling agents. Based on the results obtained above, a pretreatment, which involved two-step bis-(triethoxysilyl) ethane and gamma-aminopropyltriethoxysilane, was developed for Al substrates with commercial polyester and polyurethane paints. The results of salt spray testing, cyclic corrosion testing, and electrochemical impedance spectroscopy showed that this treatment provided the same level of corrosion performance as the treatment of phosphating plus a final chromate rinse. The likely reasons for excellent performance are discussed in terms of the physical and chemical characteristics of the

  16. Improving gas separation properties of polymeric membranes based on glassy polymers by gas phase fluorination

    NARCIS (Netherlands)

    Syrtsova, D.A.; Syrtsova, D.A.; Kharitonov, A.P.; Teplyakov, V.V.; Koops, G.H.


    The application area of existing gas separation membranes is limited by commercially available polymers for their preparation. In many cases the separation selectivity of these polymers is not sufficient for effective separation processes. One of the ways to improve the separation effectivity of

  17. Silicon nanoparticle formation depending on the discharge conditions of an atmospheric radio-frequency driven microplasma with argon/silane/hydrogen gases

    Czech Academy of Sciences Publication Activity Database

    Barwe, B.; Riedel, F.; Cibulka, Ondřej; Pelant, Ivan; Benedikt, J.


    Roč. 48, Aug (2015), s. 314001 ISSN 0022-3727 Institutional support: RVO:68378271 Keywords : silicon nanoparticles * microplasma jets * silane * atmospheric plasma * dynamic light scattering * scanning electron microscopy Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 2.772, year: 2015

  18. Formation of 9,10-phenanthrenequinone by atmospheric gas-phase reactions of phenanthrene (United States)

    Wang, Lin; Atkinson, Roger; Arey, Janet

    Phenanthrene is a 3-ring polycyclic aromatic hydrocarbon which exists mainly in the gas-phase in the atmosphere. Recent concern over the presence of 9,10-phenanthrenequinone in ambient particles led us to study the products of the gas-phase reactions of phenanthrene with hydroxyl radicals, nitrate radicals and ozone. The formation yields of 9,10-phenanthrenequinone were measured to be ˜3%, 33±9%, and ˜2% from the OH radical, NO 3 radical and O 3 reactions, respectively. Calculations suggest that daytime OH radical-initiated and nighttime NO 3 radical-initiated reactions of gas-phase phenanthrene may be significant sources of 9,10-phenanthrenequinone in ambient atmospheres. In contrast, the ozone reaction with phenanthrene is unlikely to contribute significantly to ambient 9,10-phenanthrenequinone.

  19. Measurement of pressure fluctuation in gas-liquid two-phase vortex street

    International Nuclear Information System (INIS)

    Sun Zhiqiang; Sang Wenhui; Zhang Hongjian


    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.

  20. Photoresponse of the protonated Schiff-base retinal chromophore in the gas phase

    DEFF Research Database (Denmark)

    Toker, Jonathan; Rahbek, Dennis Bo; Kiefer, H V


    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...

  1. Metal-Organic Framework Thin Films as Stationary Phases in Microfabricated Gas-Chromatography Columns.

    Energy Technology Data Exchange (ETDEWEB)

    Read, Douglas [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Sillerud, Colin Halliday [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)


    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.

  2. The Stability of CI02 as a Product of Gas Phase Decontamination Treatments

    International Nuclear Information System (INIS)

    Simmons, D. W.


    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

  3. A gas-phase reactor powered by solar energy and ethanol for H2 production

    International Nuclear Information System (INIS)

    Ampelli, Claudio; Genovese, Chiara; Passalacqua, Rosalba; Perathoner, Siglinda; Centi, Gabriele


    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

  4. Distribution of Organophosphate Esters between the Gas and Particle Phase-Model Predictions vs Measured Data. (United States)

    Sühring, Roxana; Wolschke, Hendrik; Diamond, Miriam L; Jantunen, Liisa M; Scheringer, Martin


    Gas-particle partitioning is one of the key factors that affect the environmental fate of semivolatile organic chemicals. Many organophosphate esters (OPEs) have been reported to primarily partition to particles in the atmosphere. However, because of the wide range of their physicochemical properties, it is unlikely that OPEs are mainly in the particle phase "as a class". We compared gas-particle partitioning predictions for 32 OPEs made by the commonly used OECD POV and LRTP Screening Tool ("the Tool") with the partitioning models of Junge-Pankow (J-P) and Harner-Bidleman (H-B), as well as recently measured data on OPE gas-particle partitioning. The results indicate that half of the tested OPEs partition into the gas phase. Partitioning into the gas phase seems to be determined by an octanol-air partition coefficient (log KOA) -5 (PL in Pa), as well as the total suspended particle concentration (TSP) in the sampling area. The uncertainty of the physicochemical property data of the OPEs did not change this estimate. Furthermore, the predictions by the Tool, J-P- and H-B-models agreed with recently measured OPE gas-particle partitioning.

  5. Synthesis gas demonstration plant program, Phase I. Site confirmation report

    Energy Technology Data Exchange (ETDEWEB)


    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.

  6. Multiscale and luminescent, hollow microspheres for gas phase thermometry. (United States)

    Bischoff, Lothar; Stephan, Michael; Birkel, Christina S; Litterscheid, Christian F; Dreizler, Andreas; Albert, Barbara


    Recently developed laser-based measurement techniques are used to image the temperatures and velocities in gas flows. They require new phosphor materials with an unprecedented combination of properties. A novel synthesis procedure is described here; it results in hierarchically structured, hollow microspheres of Eu 3+ -doped Y 2 O 3 , with unusual particle sizes and very good characteristics compared to full particles. Solution-based precipitation on polymer microballoons produces very stable and luminescent, ceramic materials of extremely low density. As a result of the - compared to established template-directed syntheses - reduced mass of polymer that is lost upon calcination, micron-sized particles are obtained with mesoporous walls, low defect concentrations, and nanoscale wall thicknesses. They can be produced with larger diameters (~25 µm) compared to known hollow spheres and exhibit an optimized flow behavior. Their temperature sensing properties and excellent fluidic follow-up behavior are shown by determining emission intensity ratios in a specially designed heating chamber. Emission spectroscopy and imaging, electron microscopy and X-ray diffraction results are presented for aerosolizable Y 2 O 3 with an optimized dopant concentration (8%). Challenges in the field of thermofluids can be addressed by combined application of thermometry and particle image velocimetry with such hollow microparticles.

  7. Three-dimensional, gas phase fuel cell with a laccase biocathode (United States)

    Borole, Abhijeet P.; LaBarge, Samuel; Spott, Benjamin A.

    A fuel cell using an enzymatic biocathode operating in a gas phase mode is reported. The electrode was prepared using a three-dimensional conductive electrode matrix. An enzyme solution containing laccase and a mediator was distributed into a hydrophilic matrix of carbon felt fibers creating a porous gas-flowing electrode. A Pt-based gas diffusion electrode served as the anode. A maximum power density of 9.4 W m -2 (2.9 kW m -3) was obtained with 15 U of enzyme cm -2, with hydrogen as the fuel. Power density was found to be a function of the enzyme loading, air flow rate, volume of the liquid phase and the humidity of the air stream. The ability to use methanol and ethanol as vapors in gas phase was also shown. The introduction of three-dimensionality into the electrode architecture and operation of the fuel cell in a gas phase mode to supply the fuel and the oxidant demonstrates an avenue for improving the power density of EFCs.

  8. Probing the nuclear liquid-gas phase transition

    International Nuclear Information System (INIS)

    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.


    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.)

  9. Gas phase THz spectroscopy of toxic agent simulant compounds using the AILES synchrotron beamline (United States)

    Cuisset, A.; Smirnova, I.; Bocquet, R.; Hindle, F.; Mouret, G.; Yang, C.; Pirali, O.; Roy, P.


    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.

  10. Direct gas-phase epoxidation of propylene to propylene oxide through radical reactions: A theoretical study (United States)

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


    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. (United States)

    Lee, Kyu Am; Ryoo, HeeKyoung; Ma, Byung Chol; Kim, Youngchul


    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. Product analysis of the gas-phase reaction of β-caryophyllene with ozone (United States)

    Calogirou, A.; Kotzias, D.; Kettrup, A.

    The semivolatile ketoaldehydes 3,3-dimethyl-y-methylene-2-(3-oxobutyl)-cyclobutanebutanal 1 and 3,3-dimethyl-γ-oxo-2-(3-oxobutyl)-cyclobutanebutanal 2 and formaldehyde have been identified as the main products of the reaction of ß-caryophyllene with ozone in the gas phase. In minor amounts 9-methylene-,t,12,12-trimethyl-5-oxabicyclo[]dodecane 3 was also formed. Nature and yields of these carbonyl products are discussed in terms of oxidation mechanisms involving the gas-phase reaction with ozone and OH radicals.

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

    International Nuclear Information System (INIS)

    Kleingeld, J.C.


    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. Parents of two-phase flow and theory of “gas-lift”

    Directory of Open Access Journals (Sweden)

    Zitek Pavel


    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.

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

    DEFF Research Database (Denmark)

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


    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-methylimidazolium n-octylsulfate on silica support. The Rh-sulfoxantphos SILP catalysts proved to be more regioselective than catalysts without ligand and the analogous ionic liquid-free catalysts, giving up to 96% linear product. Furthermore, the performance of the catalysts was generally...

  16. Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption. (United States)

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


    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.

  17. Studies of cluster-assembled materials: From gas phase to condensed phase (United States)

    Gao, Lin

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

  18. Diurnal variability of gas phase and surface water ethanol in southeastern North Carolina, USA (United States)

    Kieber, R. J.; Powell, J. P.; Foley, L.; Mead, R. N.; Willey, J. D.; Avery, G. B.


    Diurnal variations in gas phase and surface water concentrations of ethanol and acetaldehyde were investigated at five locations in southeastern North Carolina, USA. There were distinct diurnal oscillations observed in gas phase concentrations with maxima occurring in late afternoon suggesting that photochemical production is an important process in the cycling of these analytes in the troposphere. The rapid decrease in concentrations after the mid day maximum suggests that there is also an atmospheric photochemical sink for both analytes most likely involving photo produced hydroxyl radicals with a half-life on the order of hours rather than days at ground level. Ethanol concentrations in the surface microlayer taken at the same time as gas phase samples had a very similar diurnal profile suggesting photochemical processes, in addition to atmospheric deposition, play a role in the aqueous phase cycling of both analytes. The concentration of ethanol and acetaldehyde increased significantly in flasks containing freshwater collected from the Cape Fear River exposed to simulated sunlight for 6 h underscoring the importance of in situ photochemical production. Results of this study are significant because they represent the first simultaneous analyses of the temporal variability of ethanol and acetaldehyde concentrations in the gas and aqueous phases. These measurements are essential in order to better define the processes involved in the global biogeochemical cycling of ethanol both now and in the future as our use of the biofuel continues to grow.

  19. Phase Behavior and Physical Parameters of Natural Gas Mixture with CO2

    Directory of Open Access Journals (Sweden)

    Dali Hou


    Full Text Available The two-flash experiment, constant composition expansion experiment, saturation pressure measurement experiment, and phase transition observation experiment from well bottom hole to well head of four high CO2 content natural gas samples were carried out by using the JEFRI-PVT apparatus made from DBR Company of Canada. The experimental results show that in the four high CO2 content gas samples no phase transitions will take place at temperatures greater than 35°C. In the gas-liquid two-phase region, saturation pressures, critical pressure, critical temperature, and an integrated P-T phase diagram of different CO2 content natural gases are calculated by using the modified PR equation of state and modified (T equation proposed by Saffari. The deviations between the saturation pressure calculated by using the model proposed in this study and experimental measured saturation pressure are very small; the average relative error is only 2.86%. Thus, the model can be used to predict the phase equilibrium parameters of high CO2 content natural gas.

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

    International Nuclear Information System (INIS)

    Wu, Hao; Dong, Feng


    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

  1. New synthesis of photocurable silanes and polysiloxanes bearing heterocyclic or olefinic functions

    International Nuclear Information System (INIS)

    Youssef, B.; Lecamp, L.; Garin, S.; Bunel, C.


    In this work, we described the synthesis of silanes and polysiloxanes bearing cationic photopolymerizable groups. Two new methods were used. The first one is the reaction between 3-mercapto-propyl-1-triethoxysilane (1) and chloromethylated olefins by a phase transfer catalysis. The second one is the radical addition of (1) or poly(dimethylsiloxane-co-methylmercaptopropylsiloxane) (9) to allyl or vinyl substituted heterocyclic monomers. These methods led to the expected adducts with an excellent yield. The polysiloxanes bearing heterocyclic functional groups linked through thioether bonds were photocurable by cationic route. Under UV light intensity of 17.5 mW/cm 2 , these polymers harden after 15 or 20 s

  2. Two phases of the anyon gas and broken T symmetry

    International Nuclear Information System (INIS)

    Canright, G.S.; Rojo, A.G.


    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

  3. Isospin and momentum dependence of liquid-gas phase transition in hot asymmetric nuclear matter

    International Nuclear Information System (INIS)

    Xu, Jun; Ma, Hongru; Chen, Liewen; Li, Baoan


    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)

  4. Influence of silane coupling agents on the rheological behavior of hemp fiber filled polyamide 1010 biomass composites in molten state (United States)

    Nishitani, Yosuke; Hasumi, Megumi; Kitano, Takeshi


    In order to develop the new engineering materials such as structural materials and tribomaterials based on all plants-derived materials, the influence of silane coupling agent on the rheological properties of hemp fiber (HF) filled polyamide 1010 (PA1010) biomass composites in molten state was investigated for one step of the fabrication of these materials. PA1010 was made from sebacic acid and decamethylenediamine, which are obtained from plant-derived castor oil. Hemp fibers were surface-treated by two types of surface treatment: a) alkali treatment by NaOH solution and b) surface treatment by silane coupling agents with different concentrations. Three types of silane coupling agents: aminosilane, epoxysilane and ureidosilane were used for surface treatment. HF/PA1010 composites were extruded by a twin screw extruder and compression-molded. Rheological behavior in molten state were evaluated by oscillatory flow testing using a parallel plate type rheometer. It was found that the silane coupling agents remarkably influence on: 1) rheological properties such as storage modulus, loss modulus, loss tangent and complex viscosity in low angular frequency region in molten state, 2) temperature dependences of rheological properties, and 3) relationship between phase angle and complex modulus (van Gurp - Palmen plots). These rheological behavior were also strongly influenced by the type of silane coupling agents. The viscoelastic properties (both storage and loss moduli) of aminosilane and epoxysilane treated composites were lower, however, those of ureidosilane treated ones were higher than the moduli of only alkali treated composites. Ureidosilane treated composites were the least temperature sensitive in the surface treated composites investigated here.

  5. Oxidative potential of gas phase combustion emissions - An underestimated and potentially harmful component of air pollution from combustion processes (United States)

    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.


    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.

  6. Gas-phase spectra of MgO molecules: a possible connection from gas-phase molecules to planet formation (United States)

    Kloska, Katherine A.; Fortenberry, Ryan C.


    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.

  7. Formation routes of interstellar glycine involving carboxylic acids: possible favoritism between gas and solid phase. (United States)

    Pilling, Sergio; Baptista, Leonardo; Boechat-Roberty, Heloisa M; Andrade, Diana P P


    Despite the extensive search for glycine (NH₂CH₂COOH) and other amino acids in molecular clouds associated with star-forming regions, only upper limits have been derived from radio observations. Nevertheless, two of glycine's precursors, formic acid and acetic acid, have been abundantly detected. Although both precursors may lead to glycine formation, the efficiency of reaction depends on their abundance and survival in the presence of a radiation field. These facts could promote some favoritism in the reaction pathways in the gas phase and solid phase (ice). Glycine and these two simplest carboxylic acids are found in many meteorites. Recently, glycine was also observed in cometary samples returned by the Stardust space probe. The goal of this work was to perform theoretical calculations for several interstellar reactions involving the simplest carboxylic acids as well as the carboxyl radical (COOH) in both gas and solid (ice) phase to understand which reactions could be the most favorable to produce glycine in interstellar regions fully illuminated by soft X-rays and UV, such as star-forming regions. The calculations were performed at four different levels for the gas phase (B3LYP/6-31G*, B3LYP/6-31++G**, MP2/6-31G*, and MP2/6-31++G**) and at MP2/6-31++G** level for the solid phase (ice). The current two-body reactions (thermochemical calculation) were combined with previous experimental data on the photodissociation of carboxylic acids to promote possible favoritism for glycine formation in the scenario involving formic and acetic acid in both gas and solid phase. Given that formic acid is destroyed more in the gas phase by soft X-rays than acetic acid is, we suggest that in the gas phase the most favorable reactions are acetic acid with NH or NH₂OH. Another possible reaction involves NH₂CH₂ and COOH, one of the most-produced radicals from the photodissociation of acetic acid. In the solid phase, we suggest that the reactions of formic acid with NH

  8. Magnetic resonance velocity imaging of liquid and gas two-phase flow in packed beds. (United States)

    Sankey, M H; Holland, D J; Sederman, A J; Gladden, L F


    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.

  9. Application of 'Hydration Model' to evaluate gas phase transfer of ruthenium and technetium from reprocessing solutions

    International Nuclear Information System (INIS)

    Sasahira, Akira; Hoshikawa, Tadahiro; Kamoshida, Mamoru; Kawamura, Fumio


    In order to evaluate the amounts of gas phase transferred ruthenium (Ru), and technetium (Tc), simulations were made for the continuous evaporator used in a reprocessing plant to concentrate high level liquid waste. The concentrations and activities of nitric acid and water, which controlled the reaction rate and gas-liquid equilibrium in the evaporator solution, were evaluated using the previously developed 'Hydration Model'. When the feed solution contained 2.7 M (=mol/dm 3 ) of nitric acid, the nitric acid concentration in the evaporator solution reached its maximum at the concentration factor (CF) of 6 (CF: concentration ratio of FPs in evaporator and feed solutions). The activities of nitric acid and water were saturated at values of 0.01 and 0.43, respectively, after the CF reached 6. The simulation predicted decontamination factors DFs of 2x10 5 and 8x10 3 for Ru and Tc, respectively, for a typical evaporation conditions with an operational pressure of 6,700 Pa, and FPs of 0.02 to 1.4 M. The simulation results agreed with the verification experiment within a factor of 2 for the amount of gas-phase transferred Ru during evaporation. The factor for the amount of gas-phase transferred Tc was estimated as 5 from the measurement error in the gas-liquid equilibrium constant. (author)

  10. Gas-Phase Growth of Heterostructures of Carbon Nanotubes and Bimetallic Nanowires

    Directory of Open Access Journals (Sweden)

    Whi Dong Kim


    Full Text Available A simple, inexpensive, and viable method for growing multiple heterostructured carbon nanotubes (CNTs over the entire surface of Ni-Al bimetallic nanowires (NWs in the gas phase was developed. Polymer-templated bimetallic nitrate NWs were produced by electrospinning in the first step, and subsequent calcination resulted in the formation of bimetallic oxide NWs by thermal decomposition. In the second step, free-floating bimetallic NWs were produced by spray pyrolysis in an environment containing hydrogen gas as a reducing gas. These NWs were continuously introduced into a thermal CVD reactor in order to grow CNTs in the gas phase. Scanning electron microscopy (SEM, transmission electron microscopy (TEM, and Raman spectrometry analyses revealed that the catalytic Ni sites exposed in the non-catalytic Al matrix over the entire surface of the bimetallic NWs were seeded to radially grow highly graphitized CNTs, which resembled “foxtail” structures. The grown CNTs were found to have a relatively uniform diameter of approximately 10±2 nm and 10 to 15 walls with a hollow core. The average length of the gas-phase-grown CNTs can be controlled between 100 and 1000 nm by adjusting the residence time of the free-floating bimetallic NWs in the thermal CVD reactor.

  11. Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction. (United States)

    Zhu, Hongying; Huang, Guangming


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  13. DFT study of the reactions of Mo and Mo with CO2 in gas phase

    Indian Academy of Sciences (India)

    Abstract. Density functional theory (DFT) calculations have been performed to explore the potential energy surfaces of C–O bond activation in CO2 molecule by gas-phase Mo. + cation and Mo atom, in order to better understanding the mechanism of second-row metal reacting with CO2. The minimum energy reaction path is.

  14. Gas-phase infrared spectra of cationized nitrogen-substituted polycyclic aromatic hydrocarbons

    NARCIS (Netherlands)

    Galué, Alvaro; Pirali, O.; Oomens, J.


    Gas-phase infrared spectra of several ionized nitrogen substituted polycyclic aromatic hydrocarbons (PANHs) have been recorded in the 600-1600 cm(-1) region via IR multiple-photon dissociation (IRMPD) spectroscopy. The UV photoionized PANH ions are trapped and isolated in a quadrupole ion trap where

  15. Electron Attachment to the Gas Phase DNA Bases Cytosine and Thymine

    Czech Academy of Sciences Publication Activity Database

    Denifl, S.; Ptasiňska, S.; Probst, M.; Hrušák, Jan; Scheier, P.; Märk, T. D.


    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

  16. Gas-phase infrared spectra of cationized nitrogen-substituted polycyclic aromatic hydrocarbons

    NARCIS (Netherlands)

    Galué, H.A.; Pirali, O.; Oomens, J.


    Gas-phase infrared spectra of several ionized nitrogen substituted polycyclic aromatic hydrocarbons (PANHs) have been recorded in the 600-1600 cm-1 region via IR multiple-photon dissociation (IRMPD) spectroscopy. The UV photoionized PANH ions are trapped and isolated in a quadrupole ion trap where

  17. Gas-phase UF6 enrichment monitor for enrichment plant safeguards

    International Nuclear Information System (INIS)

    Strittmatter, R.B.; Tape, J.W.


    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

  18. Study of Iodine Behavior in the Gas Phase during a Severe Accident

    International Nuclear Information System (INIS)

    Kim, Hanchul; Cho, Yeonghun; Ryu, Myunghyun


    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

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

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


    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.

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

    NARCIS (Netherlands)

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


    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

  1. The 'sticky business' of cleaning gas-phase membrane proteins: a detergent oriented perspective. (United States)

    Borysik, Antoni J; Robinson, Carol V


    In recent years the properties of gas-phase detergent clusters have come under close scrutiny due in part to their participation in the analysis of intact membrane protein complexes by mass spectrometry. The detergent molecules that cover the protein complex are removed in the gas-phase by thermally agitating the ions by collision-induced dissociation. This process however, is not readily controlled and can frequently result in the disruption of protein structure. Improved methods of releasing proteins from detergent clusters are clearly required. To facilitate this the structural properties of detergent clusters along with the mechanistic details of their dissociation need to be understood. Pivotal to understanding the properties of gas-phase detergent clusters is the technique of ion mobility mass spectrometry. This technique can be used to assign polydisperse detergent clusters and provide information about their geometries and packing densities. In this article we consider the shapes of detergent clusters and show that these clusters possess geometries that are inconsistent with those in solution. We analyse the distributions of clusters in detail using tandem mass spectrometry and suggest that the mean charge of clusters formed from certain detergents is governed by electrostatic repulsion. We discuss the dissociation of detergent clusters and propose that detergent evaporation it a key process in the protection of protein complexes during high energy collisions in the gas-phase.

  2. How Pt nanoparticles affect TiO2-induced gas-phase photocatalytic oxidation reactions

    NARCIS (Netherlands)

    Fraters, B.D.; Amrollahi Buky, Rezvaneh; Mul, Guido


    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

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

    NARCIS (Netherlands)

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


    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

  4. Hydrogen-deuterium exchange reactions of carbanions with D2O in the gas phase

    International Nuclear Information System (INIS)

    Stewart, J.H.; Shapiro, R.H.; DePuy, C.H.; Bierbaum, V.M.


    Using the flowing afterglow technique, we have observed that carbanions participate in sequential deuterium exchange reactions with D 2 O in the gas phase. The extent of exchange is reported for 32 carbanions and the mechanism of the reaction is discussed. The usefulness of this phenomenon as a probe of the acidity and structure of anions is described

  5. Regio-Selective Intramolecular Hydrogen/Deuterium Exchange in Gas-Phase Electron Transfer Dissociation (United States)

    Hamuro, Yoshitomo


    Protein backbone amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) typically utilizes enzymatic digestion after the exchange reaction and before MS analysis to improve data resolution. Gas-phase fragmentation of a peptic fragment prior to MS analysis is a promising technique to further increase the resolution. The biggest technical challenge for this method is elimination of intramolecular hydrogen/deuterium exchange (scrambling) in the gas phase. The scrambling obscures the location of deuterium. Jørgensen's group pioneered a method to minimize the scrambling in gas-phase electron capture/transfer dissociation. Despite active investigation, the mechanism of hydrogen scrambling is not well-understood. The difficulty stems from the fact that the degree of hydrogen scrambling depends on instruments, various parameters of mass analysis, and peptide analyzed. In most hydrogen scrambling investigations, the hydrogen scrambling is measured by the percentage of scrambling in a whole molecule. This paper demonstrates that the degree of intramolecular hydrogen/deuterium exchange depends on the nature of exchangeable hydrogen sites. The deuterium on Tyr amide of neurotensin (9-13), Arg-Pro-Tyr-Ile-Leu, migrated significantly faster than that on Ile or Leu amides, indicating the loss of deuterium from the original sites is not mere randomization of hydrogen and deuterium but more site-specific phenomena. This more precise approach may help understand the mechanism of intramolecular hydrogen exchange and provide higher confidence for the parameter optimization to eliminate intramolecular hydrogen/deuterium exchange during gas-phase fragmentation.

  6. Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes

    DEFF Research Database (Denmark)

    Malcho, Phillip; Garcia-Suarez, Eduardo J.; Mentzel, Uffe Vie


    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 aromati...

  7. DFT study of the reactions of Mo and Mo with CO 2 in gas phase

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 123; Issue 3. DFT study of the reactions of Mo and Mo+ with CO2 in gas phase. Deman Han Guoliang Dai Hao Chen Hua Yan Junyong Wu Chuanfeng Wang Aiguo Zhong. Volume 123 Issue 3 May 2011 pp 299-309 ...

  8. Structure analysis of large argon clusters from gas-phase electron diffraction data: some recent results

    NARCIS (Netherlands)

    van de Waal, B.W.


    An up-to-date overview of recent developments in the structure elucidation of large ArN-clusters (103gas-phase electron diffraction data, is given. Although a satisfactory model for N3000 had been found in 1996, the size range beyond N10,000 presents new and unexpected problems.

  9. Gas-phase salt bridge interactions between glutamic acid and arginine

    NARCIS (Netherlands)

    Jaeqx, S.; Oomens, J.; Rijs, A.M.


    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

  10. Gas-phase photoemission with soft x-rays: cross sections and angular distributions

    International Nuclear Information System (INIS)

    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.


    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

  11. Ab initio study of gas phase and water-assisted tautomerization of ...

    Indian Academy of Sciences (India)


    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; ...

  12. The Significance of Gas-Phase Mass Transport in Assessment of kchem and Dchem

    DEFF Research Database (Denmark)

    Lohne, Ørjan Fossmark; Søgaard, Martin; Wiik, Kjell


    In this work, the validity of electrical conductivity relaxation (ECR) as a method for the assessment of chemical surface exchange, kchem, and bulk diffusion, Dchem, coefficients is investigated with respect to mass transport limitations in the gas phase. A model encompassing both the oxygen...

  13. Role of isospin in nuclear-matter liquid-gas phase transition

    International Nuclear Information System (INIS)

    Ducoin, C.


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

    DEFF Research Database (Denmark)

    Boll, Rebecca; Rouzee, Arnaud; Adolph, Marcus


    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...

  15. Modeling of Shale Gas Adsorption and its Influence on Phase Equilibrium

    DEFF Research Database (Denmark)

    Sandoval Lemus, Diego Rolando; Yan, Wei; Michelsen, Michael Locht


    Natural gas and oil produced from shale accounts for a signicant portion in the global production. Due to the large surface area and high organic content in shale formations, adsorption plays a major role in the storage of the hydrocarbons within the rock and their phase equilibrium. This study...

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

    International Nuclear Information System (INIS)

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


    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

  17. Gas-phase advanced oxidation for effective, efficient in situ control of pollution

    DEFF Research Database (Denmark)

    Johnson, Matthew Stanley; Nilsson, Elna Johanna Kristina; Svensson, Erik Anders


    In this article, gas-phase advanced oxidation, a new method for pollution control building on the photo-oxidation and particle formation chemistry occurring in the atmosphere, is introduced and characterized. The process uses ozone and UV-C light to produce in situ radicals to oxidize pollution...

  18. Hybrid membrane using polyethersulfone-modification of multiwalled carbon nanotubes with silane agent to enhance high performance oxygen separation

    Directory of Open Access Journals (Sweden)

    Tutuk Djoko Kusworo


    Full Text Available Mixed matrix membrane comprising carbon nanotubes embedded in polymer matrix have become one of the emerging technologies. This study was investigated in order to study the effect of silane agent modification towards carbon nanotubes (CNT surface at different concentration on oxygen enrichment performances of asymmetric mixed matrix membrane. The modified carbon nanotubes were prepared by treating the carbon nanotubes with chemical modification using Dynasylan Ameo (DA silane agent to allow PES chains to be grafted on carbon nanotubes surface. The results from the FESEM, DSC and FTIR analysis confirmed that chemical modification on carbon nanotubes surface had taken place. Sieve-in-a-cage’ morphology observed shows the poor adhesion between polymer and unmodified CNT. The gas separation performance of the asymmetric flat sheet mixed matrix membranes with modified CNT were relatively higher compared to the unmodified CNT. Hence, coated hollow fiber mixed matrix membrane with chemical modification on CNT surface using (3-aminopropyl-triethoxy methyl silane agent can potentially enhance the gas separation performance of O2 and N2.

  19. On the phase-correlation and phase-fluctuation dynamics of a strongly excited Bose gas

    Energy Technology Data Exchange (ETDEWEB)

    Sakhel, Roger R., E-mail: [Department of Basic Sciences, Faculty of Information Technology, Isra University, Amman 11622 (Jordan); The Abdus Salam International Center for Theoretical Physics, Strada Costiera 11, Trieste 34151 (Italy); Sakhel, Asaad R. [Department of Applied Sciences, Faculty of Engineering Technology, Balqa Applied University, Amman 11134 (Jordan); The Abdus Salam International Center for Theoretical Physics, Strada Costiera 11, Trieste 34151 (Italy); Ghassib, Humam B. [Department of Physics, The University of Jordan, Amman 11942 (Jordan)


    The dynamics of a Bose–Einstein condensate (BEC) is explored in the wake of a violent excitation caused by a strong time-dependent deformation of a trapping potential under the action of an intense stirring laser. The system is a two-dimensional BEC confined to a power-law trap with hard-wall boundaries. The stirring agent is a moving red-detuned laser potential. The time-dependent Gross–Pitaevskii equation is solved numerically by the split-step Crank–Nicolson method in real time. The phase correlations and phase fluctuations are examined as functions of time to demonstrate the evolving properties of a strongly-excited BEC. Of special significance is the occurrence of spatial fluctuations while the condensate is being excited. These oscillations arise from stirrer-induced density fluctuations. While the stirrer is inside the trap, a reduction in phase coherence occurs, which is attributed to phase fluctuations.

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

    International Nuclear Information System (INIS)

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


    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)

  1. Influence of structured packing on gas holdup in a three-phase bubble column

    DEFF Research Database (Denmark)

    Monsalvo, Matias Alfonso; Böhm, Ursula


    In this work, the influence of structured packing on gas holdup in gas-liquid-solid dispersions has been studied. The experiments were carried out in an empty column and in column containing structured packing operating under identical conditions. Glass beads and silicon carbide particles were used...... as the solid material and the volumetric fraction of solids was varied from 0% to around 10%. The liquid viscosity was strongly modified using water, CMC solution and glycerol. The experimental results obtained with both columns were compared with previous results obtained in two-phase bubble columns...... the results obtained with glycerol, these correlations can predict the gas holdup of three-phase bubble columns with reasonable accuracy. (C) 2007 Elsevier Ltd. All rights reserved....

  2. Finite-time thermodynamics and the gas-liquid phase transition. (United States)

    Santoro, M; Schön, J C; Jansen, M


    In this paper, we study the application of the concept of finite-time thermodynamics to first-order phase transitions. As an example, we investigate the transition from the gaseous to the liquid state by modeling the liquification of the gas in a finite time. In particular, we introduce, state, and solve an optimal control problem in which we aim at achieving the gas-liquid first-order phase transition through supersaturation within a fixed time in an optimal fashion, in the sense that the work required to supersaturate the gas, called excess work, is minimized by controlling the appropriate thermodynamic parameters. The resulting set of coupled nonlinear differential equations is then solved for three systems, nitrogen N2, oxygen O2, and water vapor H2O.

  3. Partitioning of phthalates among the gas phase, airborne particles and settled dust in indoor environments

    DEFF Research Database (Denmark)

    Weschler, Charles J.; Salthammer, Tunga; Fromme, Hermann


    A critical evaluation of human exposure to phthalate esters in indoor environments requires the determination of their distribution among the gas phase, airborne particles and settled dust. If sorption from the gas phase is the dominant mechanism whereby a given phthalate is associated with both...... airborne particles and settled dust, there should be a predictable relationship between its particle and dust concentrations. The present paper tests this for six phthalate esters (DMP, DEP, DnBP, DiBP, BBzP and DEHP) that have been measured in both the air and the settled dust of 30 Berlin apartments....... The particle concentration, C-particle, of a given phthalate was calculated from its total airborne concentration and the concentration of airborne particles (PM4). This required knowledge of the particle-gas partition coefficient, K., which was estimated from either the saturation vapor pressure (p...

  4. Method and apparatus for forming a carbon-silicon bond in a silane (United States)

    Schattenmann, Florian Johannes


    A method for forming at least one product silane, comprising reacting a transition metal hydride with a starting silane in a presence of a catalyst and at a temperature that exceeds a threshold temperature associated with said reacting.

  5. Measurement of gas hold-up in three-phase systems by ultrasonic technique

    Energy Technology Data Exchange (ETDEWEB)

    Maezawa, Akinori (Graduate School of Electronic Science and Technology, Shizuoka Univ., Hamamatsu (Japan)); Muramatsu, Shingo (Dept. of Chemical Engineering, Shizuoka Univ., Hamamatsu (Japan)); Uchida, Shigeo (Dept. of Chemical Engineering, Shizuoka Univ., Hamamatsu (Japan)); Okamura, Seichi (Dept. of Electronic Engineering, Shizuoka Univ., Hamamatsu (Japan))


    It was established by using double impulse method that the transmission time of an ultrasonic wave, which passes near a bubble, is either shorter or longer than that in the liquid system. This is attributed to the fluid vortex originated by the bubble rising ahead of the wave. The longitudinal distribution of gas hold-up in a three-phase system, measured by analyzing wave shape and reduction of transmission time is in good agreement with that obtained by using the static pressure method. This indicates the possibility of application of ultrasonic techniques to the simultaneous measurement of phase hold-ups in the three-phase system. (orig.)

  6. Comparative simulation study of gas-phase propylene polymerization in fluidized bed reactors using aspen polymers and two phase models

    Directory of Open Access Journals (Sweden)

    Shamiria Ahmad


    Full Text Available A comparative study describing gas-phase propylene polymerization in fluidized-bed reactors using Ziegler-Natta catalyst is presented. The reactor behavior was explained using a two-phase model (which is based on principles of fluidization as well as simulation using the Aspen Polymers process simulator. The two-phase reactor model accounts for the emulsion and bubble phases which contain different portions of catalysts with the polymerization occurring in both phases. Both models predict production rate, molecular weight, polydispersity index (PDI and melt flow index (MFI of the polymer. We used both models to investigate the effect of important polymerization parameters, namely catalyst feed rate and hydrogen concentration, on the product polypropylene properties, such as production rate, molecular weight, PDI and MFI. Both the two-phase model and Aspen Polymers simulator showed good agreement in terms of production rate. However, the models differed in their predictions for weight-average molecular weight, PDI and MFI. Based on these results, we propose incorporating the missing hydrodynamic effects into Aspen Polymers to provide a more realistic understanding of the phenomena encountered in fluidized bed reactors for polyolefin production.

  7. Preparation and Characterization of Silanes Films to Protect Electrogalvanized Steel (United States)

    Seré, Pablo R.; Egli, Walter; Di Sarli, Alejandro R.; Deyá, Cecilia


    Silanes are an interesting alternative to chromate-based surface treatments for temporary protection of electrogalvanized steel. In this work, the protective behavior of 3-mercaptopropyltrimethoxysilane (MTMO), 3-aminopropyltriethoxysilane (AMEO), or 3-glycidoxypropyltrimethoxysilane (GLYMO) films applied on electrogalvanized automotive quality steel sheets has been studied. The silane coating morphology, composition, and porosity were characterized by scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS), x-ray fluorescence, immersion in copper sulfate, and cyclic voltammetry. The corrosion protection was evaluated by polarization curves, electrochemical noise measurements, electrochemical impedance spectrometry, and accelerated humidity chamber tests. The results showed that the silanes protect temporarily electrogalvanized steel from corrosion. MTMO forms a relatively thick and cracked film. AMEO and GLYMO films were so thin that they could not be observed by SEM but silicon was detected by EDS. MTMO provided good temporary protection, being an alternative to replace Cr(VI) as protector of electrogalvanized steel.

  8. Are ionic liquids pairwise in gas phase? A cluster approach and in situ IR study. (United States)

    Dong, Kun; Zhao, Lidong; Wang, Qian; Song, Yuting; Zhang, Suojiang


    In this work, we discussed the vaporization and gas species of ionic liquids (ILs) by a cluster approach of quantum statistical thermodynamics proposed by R. Luwig (Phys. Chem. Chem. Phys., 10, 4333), which is a controversial issue up to date. Based on the different sized clusters (2-12 ion-pairs) of the condensed phase, the molar enthalpies of vaporization (ΔvapH, 298.15 K, 1bar) of four representative ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][NTf2]) 1-ethyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([Emmim][NTf2]) 1-ethyl-3-methylimidazolium chloride ([Emim]Cl) and ethylammonium nitrate ([EtAm][NO3]), were calculated. The predicted ΔvapH were increased remarkably; even the values of [EtAm][NO3] were larger than 700 kJ mol(-1) when the charged isolated ions were assumed to be gas species. However, the ΔvapH were close to experimental measurements when the gas species assumed to be anion-cation pairwise, indicating that the different conformational ion-pairs can coexist in the gas phase when the IL is evaporated. Particularly for the protic IL, [EtAm][NO3], even the neutral precursor molecules by proton transfer can occur in gas phase. In addition, it's found that the effect of hydrogen bonds on the vaporization cannot be negligible by comparing the ΔvapH of [Emim][NTf2] with [Emmim][NTf2]. The in situ and calculated IR spectra provided the further proof that the ions are pairwise in gas phase.

  9. The Genealogical Tree of Ethanol: Gas-phase Formation of Glycolaldehyde, Acetic Acid, and Formic Acid (United States)

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


    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.

  10. Gas-phase metalloprotein complexes interrogated by ion mobility-mass spectrometry (United States)

    Faull, Peter A.; Korkeila, Karoliina E.; Kalapothakis, Jason M.; Gray, Andrew; McCullough, Bryan J.; Barran, Perdita E.


    Gas-phase biomolecular structure may be explored through a number of analytical techniques. Ion mobility-mass spectrometry (IM-MS) continues to prove itself as a sensitive and reliable bioanalytical tool for gas-phase structure determination due to intense study and development over the past 15 years. A vast amount of research interest, especially in protein and peptide conformational studies has generated a wealth of structural information for biological systems from small peptides to megadalton-sized biomolecules. In this work, linear low field IM-MS has been used to study gas-phase conformations and determine rotationally averaged collision cross-sections of three metalloproteins--cytochrome c, haemoglobin and calmodulin. Measurements have been performed on the MoQToF, a modified QToF 1 instrument (Micromass UK Ltd., Manchester, UK) modified in house. Gas-phase conformations and cross-sections of multimeric cytochrome c ions of the form [xM + nH+]n+ for x = 1-3 (monomer to trimer) have been successfully characterised and measured. We believe these to be the first reported collision cross-sections of higher order multimeric cytochrome c. Haemoglobin is investigated to obtain structural information on the associative mechanism of tetramer formation. Haemoglobin molecules, comprising apo- and holo-monomer chains, dimer and tetramer are transferred to the gas phase under a range of solution conditions. Structural information on the proposed critical intermediate, semi-haemoglobin, is reported. Cross-sections of the calcium binding protein calmodulin have been obtained under a range of calcium-bound conditions. Metalloprotein collision cross-sections from ion mobility measurements are compared with computationally derived values from published NMR and X-ray crystallography structural data. Finally we consider the change in the density of the experimentally measured rotationally averaged collision cross-section for compact geometries of the electrosprayed proteins.

  11. Diffusion Monte Carlo simulations of gas phase and adsorbed D2-(H2)n clusters (United States)

    Curotto, E.; Mella, M.


    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.

  12. Product energy deposition of CN + alkane H abstraction reactions in gas and solution phases (United States)

    Glowacki, David R.; Orr-Ewing, Andrew J.; Harvey, Jeremy N.


    In this work, we report the first theoretical studies of post-transition state dynamics for reaction of CN with polyatomic organic species. Using electronic structure theory, a newly developed analytic reactive PES, a recently implemented rare-event acceleration algorithm, and a normal mode projection scheme, we carried out and analyzed quasi-classical and classical non-equilibrium molecular dynamics simulations of the reactions CN + propane (R1) and CN + cyclohexane (R2). For (R2), we carried out simulations in both the gas phase and in a CH2Cl2 solvent. Analysis of the results suggests that the solvent perturbations to the (R2) reactive free energy surface are small, leading to product energy partitioning in the solvent that is similar to the gas phase. The distribution of molecular geometries at the respective gas and solution phase variational association transition states is very similar, leading to nascent HCN which is vibrationally excited in both its CH stretching and HCN bending coordinates. This study highlights the fact that significant non-equilibrium energy distributions may follow in the wake of solution phase bimolecular reactions, and may persist for hundreds of picoseconds despite frictional damping. Consideration of non-thermal distributions is often neglected in descriptions of condensed-phase reactivity; the extent to which the present intriguing observations are widespread remains an interesting question.

  13. Lattice model theory of the equation of state covering the gas, liquid, and solid phases (United States)

    Bonavito, N. L.; Tanaka, T.; Chan, E. M.; Horiguchi, T.; Foreman, J. C.


    The three stable states of matter and the corresponding phase transitions were obtained with a single model. Patterned after Lennard-Jones and Devonshires's theory, a simple cubic lattice model containing two fcc sublattices (alpha and beta) is adopted. The interatomic potential is taken to be the Lennard-Jones (6-12) potential. Employing the cluster variation method, the Weiss and the pair approximations on the lattice gas failed to give the correct phase diagrams. Hybrid approximations were devised to describe the lattice term in the free energy. A lattice vibration term corresponding to a free volume correction is included semi-phenomenologically. The combinations of the lattice part and the free volume part yield the three states and the proper phase diagrams. To determine the coexistence regions, the equalities of the pressure and Gibbs free energy per molecule of the coexisting phases were utilized. The ordered branch of the free energy gives rise to the solid phase while the disordered branch yields the gas and liquid phases. It is observed that the triple point and the critical point quantities, the phase diagrams and the coexistence regions plotted are in good agreement with the experimental values and graphs for argon.

  14. The Effect of Silane Coupling Agents on a Composite Polyamide-6/Talc

    Directory of Open Access Journals (Sweden)

    H. Wiebeck


    Full Text Available This paper evaluates the effect of the addition of silane agents on the mechanical properties (tensile strength, hardness and flexibility of the composite polyamide-6/talc. For this purpose, 30% and 40% of a talc with and without the addition of silane agents were incorporated into polyamide-6. Three kinds of silane agents were used, resulting in nine formulations. Comparing the experimental results, it is concluded that the silane agents improve the mechanical properties of the composite material.

  15. Effect of duty-cycles on the air plasma gas-phase of dielectric barrier discharges (United States)

    Barni, R.; Biganzoli, I.; Dell'Orto, E. C.; Riccardi, C.


    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.

  16. Silane pre-treatments on copper and aluminium

    International Nuclear Information System (INIS)

    Deflorian, F.; Rossi, S.; Fedrizzi, L.


    A large part of aluminium products are coated with an organic layer in order to improve the corrosion resistance. Copper surfaces are also sometimes protected with an organic coating to improve the durability or the aesthetic properties. Examples of industrial applications are household appliances and heat exchanger components. For these applications it is not rare to have the industrial need to treat at the same time components made of aluminium and copper. In order to extend the service life of the organic coated copper a specific surface pre-treatment is often required. Nevertheless, probably because of the limited market of this application, no specific pre-treatments for copper are industrially developed, with the exception of cleaning procedures, but simply extensions of existing pre-treatments optimised for other metals (aluminium, zinc) are used. The application of silane pre-treatments as adhesion promoters for organic coated metals is remarkably increasing in the last decade, because silanes offer very good performance together with high environmental compatibility. The idea is therefore to try to develop a specific silane based pre-treatment for copper. The starting point is the existing silane products for aluminium, optimising the composition and the application conditions (concentration, temperature, pH of the bath, etc.) in order to develop a high performance copper alloy pre-treatment increasing the protective properties and the adhesion of a successively applied organic coating. Moreover these pre-treatments could be used for aluminium alloys too and therefore could be suggested for multi-metals components. The deposits were analysed using FTIR spectroscopy and optical and electron microscopic observations. A careful electrochemical characterisation, mainly by electrochemical impedance spectroscopy measurements (EIS) was carried out to highlight the presence of silane and to evaluate the performance of the different deposits. In order to study an

  17. Site-specific analysis of gas-phase hydrogen/deuterium exchange of peptides and proteins by electron transfer dissociation. (United States)

    Rand, Kasper D; Pringle, Steven D; Morris, Michael; Brown, Jeffery M


    To interpret the wealth of information contained in the hydrogen/deuterium exchange (HDX) behavior of peptides and proteins in the gas-phase, analytical tools are needed to resolve the HDX of individual exchanging sites. Here we show that ETD can be combined with fast gas-phase HDX in ND(3) gas and used to monitor the exchange of side-chain hydrogens of individual residues in both small peptide ions and larger protein ions a few milliseconds after electrospray. By employing consecutive traveling wave ion guides in a mass spectrometer, peptide and protein ions were labeled on-the-fly (0.1-10 ms) in ND(3) gas and subsequently fragmented by ETD. Fragment ions were separated using ion mobility and mass analysis enabled the determination of the gas-phase deuterium uptake of individual side-chain sites in a range of model peptides of different size and sequence as well as two proteins; cytochrome C and ubiquitin. Gas-phase HDX-ETD experiments on ubiquitin ions ionized from both denaturing and native solution conditions suggest that residue-specific HDX of side-chain hydrogens is sensitive to secondary and tertiary structural features occurring in both near-native and unfolded gas-phase conformers present shortly after electrospray. The described approach for online gas-phase HDX and ETD paves the way for making mass spectrometry techniques based on gas-phase HDX more applicable in bioanalytical research.

  18. 40 CFR 721.9500 - Silane, (1,1-dimethylethoxy) dimethoxy(2-methyl propyl)-. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Silane, (1,1-dimethylethoxy) dimethoxy... New Uses for Specific Chemical Substances § 721.9500 Silane, (1,1-dimethylethoxy) dimethoxy(2-methyl... substance silane, (1,1-dimethylethoxy) dimethoxy (2-methylpropyl)- (PMN P-89-906) is subject to reporting...

  19. 40 CFR 721.9501 - Silane, triethoxy[3-oxiranylmethoxy)propyl]-. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Silane, triethoxy -. 721.9501 Section... Substances § 721.9501 Silane, triethoxy -. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as silane, triethoxy - (PMN P-01-781; CAS No. 2602-34-2) is...

  20. Density-driven transport of gas phase chemicals in unsaturated soils. (United States)

    Fen, Chiu-Shia; Sun, Yong-Tai; Cheng, Yuen; Chen, Yuanchin; Yang, Whaiwan; Pan, Changtai


    Variations of gas phase density are responsible for advective and diffusive transports of organic vapors in unsaturated soils. Laboratory experiments were conducted to explore dense gas transport (sulfur hexafluoride, SF 6 ) from different source densities through a nitrogen gas-dry soil column. Gas pressures and SF 6 densities at transient state were measured along the soil column for three transport configurations (horizontal, vertically upward and vertically downward transport). These measurements and others reported in the literature were compared with simulation results obtained from two models based on different diffusion approaches: the dusty gas model (DGM) equations and a Fickian-type molar fraction-based diffusion expression. The results show that the DGM and Fickian-based models predicted similar dense gas density profiles which matched the measured data well for horizontal transport of dense gas at low to high source densities, despite the pressure variations predicted in the soil column were opposite to the measurements. The pressure evolutions predicted by both models were in trend similar to the measured ones for vertical transport of dense gas. However, differences between the dense gas densities predicted by the DGM and Fickian-based models were discernible for vertically upward transport of dense gas even at low source densities, as the DGM-based predictions matched the measured data better than the Fickian results did. For vertically downward transport, the dense gas densities predicted by both models were not greatly different from our experimental measurements, but substantially greater than the observations obtained from the literature, especially at high source densities. Further research will be necessary for exploring factors affecting downward transport of dense gas in soil columns. Use of the measured data to compute flux components of SF 6 showed that the magnitudes of diffusive flux component based on the Fickian-type diffusion

  1. Gas phase collision dynamics by means of pulse-radiolysis methods

    International Nuclear Information System (INIS)

    Hatano, Yoshihiko


    After a brief survey of recent advances in gas-phase collision dynamics studies using pulse radiolysis methods, the following two topics in our research programs are presented with emphasis on the superior advantages of the pulse radiolysis methods over the various methods of gas-phase collision dynamics, such as beam methods, swarm methods and flow methods. One of the topics is electron attachment to van der Waals molecules. The attachment rates of thermal electrons to O 2 and other molecules in dense gases have been measured in wide ranges of both gas temperatures and pressures, from which experimental evidence has been obtained for electron attachment to van der Waals molecules. The results have been compared with theories and discussed in terms of the effect of van der Waals interaction on the electron attachment resonance. The obtained conclusions have been related with investigations of electron attachment, solvation and localization in the condensed phase. The other is Penning ionization and its related processes. The rate constants for the de-excitation of He(2 1 P), He(2 3 S), Ne( 3 P 0 ), Ne( 3 P 1 ), Ne( 3 P 2 ), Ar( 1 P 1 ), Ar( 3 P 1 ), by atoms and molecules have been measured in the temperature range from 100 to 300 K, thus obtaining the collisional energy dependence of the de-excitation cross sections. The results are compared in detail with theories classified according to the excited rare gas atoms in the metastable and resonance states. (author)

  2. Gas-phase advanced oxidation as an integrated air pollution control technique

    Directory of Open Access Journals (Sweden)

    Getachew A. Adnew


    Full Text Available Gas-phase advanced oxidation (GPAO is an emerging air cleaning technology based on the natural self-cleaning processes that occur in the Earth’s atmosphere. The technology uses ozone, UV-C lamps and water vapor to generate gas-phase hydroxyl radicals that initiate oxidation of a wide range of pollutants. In this study four types of GPAO systems are presented: a laboratory scale prototype, a shipping container prototype, a modular prototype, and commercial scale GPAO installations. The GPAO systems treat volatile organic compounds, reduced sulfur compounds, amines, ozone, nitrogen oxides, particles and odor. While the method covers a wide range of pollutants, effective treatment becomes difficult when temperature is outside the range of 0 to 80 °C, for anoxic gas streams and for pollution loads exceeding ca. 1000 ppm. Air residence time in the system and the rate of reaction of a given pollutant with hydroxyl radicals determine the removal efficiency of GPAO. For gas phase compounds and odors including VOCs (e.g. C6H6 and C3H8 and reduced sulfur compounds (e.g. H2S and CH3SH, removal efficiencies exceed 80%. The method is energy efficient relative to many established technologies and is applicable to pollutants emitted from diverse sources including food processing, foundries, water treatment, biofuel generation, and petrochemical industries.

  3. Laboratory Measurements of Gas Phase Pyrolysis Products from Southern Wildland Fuels using Infrared Spectroscopy (United States)

    Scharko, N.; Safdari, S.; Danby, T. O.; Howarth, J.; Beiswenger, T. N.; Weise, D.; Myers, T. L.; Fletcher, T. H.; Johnson, T. J.


    Combustion is an oxidation reaction that occurs when there is less fuel available than oxidizers, while pyrolysis is a thermal decomposition process that occurs under "fuel rich" conditions where all of the available oxidizers are consumed leaving some fuel(s) either unreacted or partially reacted. Gas-phase combustion products from biomass burning experiments have been studied extensively; less is known, however, about pyrolysis processes and products. Pyrolysis is the initial reaction occurring in the burning process and generates products that are subsequently oxidized during combustion, yielding highly-oxidized chemicals. This laboratory study investigates the pyrolysis processes by using an FTIR spectrometer to detect and quantify the gas-phase products from thermal decomposition of intact understory fuels from forests in the southeastern United States. In particular, a laboratory flat-flame burner operating under fuel rich conditions (no oxygen) was used to heat individual leaves to cause decomposition. The gas-phase products were introduced to an 8 meter gas cell coupled to an infrared spectrometer were used to monitor the products. Trace gas emissions along with emission ratios, which are calculated by dividing the change in the amount of the trace gas by the change in the amount of CO, for the plant species, gallberry (Ilex glabra) and swampbay (Persea palustris) were determined. Preliminary measurements observed species such as CO2, CO, C2H2, C2H4, HCHO, CH3OH, isoprene, 1,3-butadiene, phenol and NH3 being produced as part of the thermal decomposition process. It is important to note that FTIR will not detect H2.

  4. Experiments and Phase-field Modeling of Hydrate Growth at the Interface of Migrating Gas Fingers (United States)

    Fu, X.; Jimenez-Martinez, J.; Porter, M. L.; Cueto-Felgueroso, L.; Juanes, R.


    The fate of methane bubbles escaping from seafloor seeps remains an important research question, as it directly concerns our understanding of the impact of seafloor methane leakage on ocean biogeochemistry. While the physics of rising bubbles in a water column has been studied extensively, the process is poorly understood when the gas bubbles form a hydrate ``crust" during their ascent. Understanding bubble rise, expansion and dissolution under these conditions is essential to determine the fate of bubble plumes of hydrate-forming gases such as methane and carbon dioxide from natural and man-made accidental releases. Here, we first present experimental observations of the dynamics of a bubble of Xenon in a water-filled and pressurized Hele-Shaw cell. The evolution is controlled by two processes: (1) the formation of a hydrate "crust" around the bubble, and (2) viscous fingering from bubble expansion (Figure 1). To reproduce the experimental observations, we propose a phase-field model that describes the nucleation and thickening of a porous solid shell on a moving gas-liquid interface. We design the free energy of the three-phase system (gas-liquid-hydrate) to rigorously account for interfacial effects, mutual solubility, and phase transformations (hydrate formation and disappearance). We introduce a pseudo-plasticity model with large viscosity variations to describe the plate-like rheology of the hydrate shell. We present high-resolution numerical simulations of the model, which illustrate the emergence of complex "crustal fingering" patterns as a result of gas fingering dynamics modulated by hydrate growth at the interface. Figure caption: Snapshot of the Hele-Shaw cell experiment. As the bubble expands from depressurization of the cell, gas fingers move through the liquid and Xe-hydrate readily forms at the gas-liquid interface, giving rise to complex "crustal fingering" patterns.

  5. Investigation of gas-phase decontamination of internally radioactively contaminated gaseous diffusion process equipment and piping

    International Nuclear Information System (INIS)

    Bundy, R.D.; Munday, E.B.


    Construction of the gaseous diffusion plants (GDPs) was begun during World War 2 to produce enriched uranium for defense purposes. These plants, which utilized UF 6 gas, were used primarily for this purpose through 1964. From 1959 through 1968, production shifted primarily to uranium enrichment to supply the nuclear power industry. Additional UF 6 -handling facilities were built in feed and fuel-processing plants associated with the uranium enrichment process. Two of the five process buildings at Oak ridge were shut down in 1964. Uranium enrichment activities at Oak Ridge were discontinued altogether in 1985. In 1987, the Department of Energy (DOE) decided to proceed with a permanent shutdown of the Oak Ridge Gaseous Diffusion Plant (ORGDP). DOE intends to begin decommissioning and decontamination (D ampersand D) of ORGDP early in the next century. The remaining two GDPs are expected to be shut down during the next 10 to 40 years and will also require D ampersand D, as will the other UF 6 -handling facilities. This paper presents an investigation of gas- phase decontamination of internally radioactively contaminated gaseous diffusion process equipment and piping using powerful fluorinating reagents that convert nonvolatile uranium compounds to volatile UF 6 . These reagents include ClF 3 , F 2 , and other compounds. The scope of D ampersand D at the GDPs, previous work of gas-phase decontamination, four concepts for using gas-phase decontamination, plans for further study of gas-phase decontamination, and the current status of this work are discussed. 13 refs., 15 figs

  6. Liquid-gas phase transition in strange hadronic matter with relativistic models (United States)

    Torres, James R.; Gulminelli, F.; Menezes, Débora P.


    Background: The advent of new dedicated experimental programs on hyperon physics is rapidly boosting the field, and the possibility of synthesizing multiple strange hypernuclei requires the addition of the strangeness degree of freedom to the models dedicated to nuclear structure and nuclear matter studies at low energy. Purpose: We want to settle the influence of strangeness on the nuclear liquid-gas phase transition. Because of the large uncertainties concerning the hyperon sector, we do not aim at a quantitative estimation of the phase diagram but rather at a qualitative description of the phenomenology, as model independent as possible. Method: We analyze the phase diagram of low-density matter composed of neutrons, protons, and Λ hyperons using a relativistic mean field (RMF) model. We largely explore the parameter space to pin down generic features of the phase transition, and compare the results to ab initio quantum Monte Carlo calculations. Results: We show that the liquid-gas phase transition is only slightly quenched by the addition of hyperons. Strangeness is seen to be an order parameter of the phase transition, meaning that dilute strange matter is expected to be unstable with respect to the formation of hyperclusters. Conclusions: More quantitative results within the RMF model need improved functionals at low density, possibly fitted to ab initio calculations of nuclear and Λ matter.

  7. Comprehensive Gas-Phase Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 2. Gas-Phase Hydrogen/Deuterium Exchange for Ion Population Estimation (United States)

    Khakinejad, Mahdiar; Ghassabi Kondalaji, Samaneh; Tafreshian, Amirmahdi; Valentine, Stephen J.


    Gas-phase hydrogen/deuterium exchange (HDX) using D2O reagent and collision cross-section (CCS) measurements are utilized to monitor the ion conformers of the model peptide acetyl-PAAAAKAAAAKAAAAKAAAAK. The measurements are carried out on a home-built ion mobility instrument coupled to a linear ion trap mass spectrometer containing electron transfer dissociation (ETD) capabilities. ETD is utilized to obtain per-residue deuterium uptake data for select ion conformers, and a new algorithm is presented for interpreting the HDX data. Using molecular dynamics (MD) production data and a hydrogen accessibility scoring (HAS)-number of effective collisions (NEC) model, hypothetical HDX behavior is attributed to various in-silico candidate (CCS match) structures. The HAS-NEC model is applied to all candidate structures, and non-negative linear regression is employed to determine structure contributions resulting in the best match to deuterium uptake. The accuracy of the HAS-NEC model is tested with the comparison of predicted and experimental isotopic envelopes for several of the observed c-ions. It is proposed that gas-phase HDX can be utilized effectively as a second criterion (after CCS matching) for filtering suitable MD candidate structures. In this study, the second step of structure elucidation, 13 nominal structures were selected (from a pool of 300 candidate structures) and each with a population contribution proposed for these ions.

  8. Gas-Phase Oxidation of Aqueous Ethanol by Nanoparticle Vanadia/Anatase Catalysts

    DEFF Research Database (Denmark)

    Jørgensen, Betina; Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas


    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...... quantitative conversion at 175-200 A degrees C. Furthermore, a selectivity above 80% for acetic acid could be achieved at low gas hourly space velocity at temperatures as low as 165 A degrees C....

  9. Review: gas-phase ion chemistry of the noble gases: recent advances and future perspectives. (United States)

    Grandinetti, Felice


    This review article surveys recent experimental and theoretical advances in the gas-phase ion chemistry of the noble gases. Covered issues include the interaction of the noble gases with metal and non-metal cations, the conceivable existence of covalent noble-gas anions, the occurrence of ion-molecule reactions involving singly-charged xenon cations, and the occurrence of bond-forming reactions involving doubly-charged cations. Research themes are also highlighted, that are expected to attract further interest in the future.

  10. Phase diagrams for an ideal gas mixture of fermionic atoms and bosonic molecules

    DEFF Research Database (Denmark)

    Williams, J. E.; Nygaard, Nicolai; Clark, C. W.


    We calculate the phase diagrams for a harmonically trapped ideal gas mixture of fermionic atoms and bosonic molecules in chemical and thermal equilibrium, where the internal energy of the molecules can be adjusted relative to that of the atoms by use of a tunable Feshbach resonance. We plot...... diagrams obtained in recent experiments on the Bose-Einstein condensation to Bardeen-Cooper-Schrieffer crossover, in which the condensate fraction is plotted as a function of the initial temperature of the Fermi gas measured before a sweep of the magnetic field through the resonance region....

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

    Directory of Open Access Journals (Sweden)

    V. V. Perevezentsev


    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.

  12. Beyond phthalates: Gas phase concentrations and modeled gas/particle distribution of modern plasticizers

    Energy Technology Data Exchange (ETDEWEB)

    Schossler, Patricia [Fraunhofer WKI, Department of Material Analysis and Indoor Chemistry, Bienroder Weg 54E, D-38108 Braunschweig (Germany); Institute of Environmental and Sustainable Chemistry, Technische Universitaet Braunschweig, Hagenring 30, D-38106 Braunschweig (Germany); Schripp, Tobias, E-mail: [Fraunhofer WKI, Department of Material Analysis and Indoor Chemistry, Bienroder Weg 54E, D-38108 Braunschweig (Germany); Salthammer, Tunga [Fraunhofer WKI, Department of Material Analysis and Indoor Chemistry, Bienroder Weg 54E, D-38108 Braunschweig (Germany); Bahadir, Muefit [Institute of Environmental and Sustainable Chemistry, Technische Universitaet Braunschweig, Hagenring 30, D-38106 Braunschweig (Germany)


    The ongoing health debate about polymer plasticizers based on the esters of phthalic acid, especially di(2-ethylhexyl) phthalate (DEHP), has caused a trend towards using phthalates of lower volatility such as diisononyl phthalate (DINP) and towards other acid esters, such as adipates, terephthalates, citrates, etc. Probably the most important of these so-called 'alternative' plasticizers is diisononyl cyclohexane-1,2-dicarboxylate (DINCH). In the indoor environment, the continuously growing market share of this compound since its launch in 2002 is inter alia apparent from the increasing concentration of DINCH in settled house dust. From the epidemiological point of view there is considerable interest in identifying how semi-volatile organic compounds (SVOCs) distribute in the indoor environment, especially in air, airborne particles and sedimented house dust. This, however, requires reliable experimental concentration data for the different media and good measurements or estimates of their physical and chemical properties. This paper reports on air concentrations for DINP, DINCH, diisobutyl phthalate (DIBP), diisobutyl adipate (DIBA), diisobutyl succinate (DIBS) and diisobutyl glutarate (DIBG) from emission studies in the Field and Laboratory Emission Cell (FLEC). For DINP and DINCH it took about 50 days to reach the steady-state value: for four months no decay in the concentration could be observed. Moreover, vapor pressures p{sub 0} and octanol-air partitioning coefficients K{sub OA} were obtained for 37 phthalate and non-phthalate plasticizers from two different algorithms: EPI Suite and SPARC. It is shown that calculated gas/particle partition coefficients K{sub p} and fractions can widely differ due to the uncertainty in the predicted p{sub 0} and K{sub OA} values. For most of the investigated compounds reliable experimental vapor pressures are not available. Rough estimates can be obtained from the measured emission rate of the pure compound in a

  13. Novel gas holdup and regime transition correlation for two-phase bubble columns (United States)

    Besagni, G.; Inzoli, F.


    The gas holdup is dimensionless parameter of fundamental and practical importance in the operation, design and scale-up of bubble columns. Unfortunately, the many relationships between the bubble column fluid dynamic parameters and the various variables characterizing the system make it difficult to find general correlations for the precise estimation of the gas holdup. Wilkinson et al. (1992), in their pioneering paper, proposed a correlation to predict the gas holdup in industrial-scale bubble columns, based on the physical properties of the phases and the operating conditions. However, this correlation lacks in generality, as it does not take in account the bubble column design. In this paper, we propose a generalization of the Wilkinson et al. (1992) gas holdup correlation to take into also the bubble column design parameters. Starting from considerations concerning the flow regime transition, corrective parameters are included to account for the effects introduced by the gas sparger openings, the bubble column aspect ratio and the bubble column diameter. The proposed correlation has been found to predict fairly well previously published gas holdup and flow regime transition data.

  14. CFD simulation of gas and non-Newtonian fluid two-phase flow in anaerobic digesters. (United States)

    Wu, Binxin


    This paper presents an Eulerian multiphase flow model that characterizes gas mixing in anaerobic digesters. In the model development, liquid manure is assumed to be water or a non-Newtonian fluid that is dependent on total solids (TS) concentration. To establish the appropriate models for different TS levels, twelve turbulence models are evaluated by comparing the frictional pressure drops of gas and non-Newtonian fluid two-phase flow in a horizontal pipe obtained from computational fluid dynamics (CFD) with those from a correlation analysis. The commercial CFD software, Fluent12.0, is employed to simulate the multiphase flow in the digesters. The simulation results in a small-sized digester are validated against the experimental data from literature. Comparison of two gas mixing designs in a medium-sized digester demonstrates that mixing intensity is insensitive to the TS in confined gas mixing, whereas there are significant decreases with increases of TS in unconfined gas mixing. Moreover, comparison of three mixing methods indicates that gas mixing is more efficient than mixing by pumped circulation while it is less efficient than mechanical mixing.

  15. Fractionation of Hydrocarbons Between Oil and Gas Phases Fractionnement des hydrocarbures entre les phases huile et gaz

    Directory of Open Access Journals (Sweden)

    Ruffier-Meray V.


    Full Text Available The investigation of hydrocarbon fractionation between oil and gas phases is of interest for several purposes in reservoir exploitation. In reservoir geochemistry, the evolution of light hydrocarbon fractions of oils may explain some migration phenomena. In gas injection projects, the preferred dissolution of some components in gas may alter the composition as well as the properties of the oil. Underground gas storage in depleted oil reservoirs may also be concerned by these problems. Results of several IFP studies are described here to illustrate and to quantify the phenomenon. Two of them, using real reservoir fluids, concern reservoir geochemistry, while the third, which is a swelling test, aimed to study gas injection, investigated a synthetic reservoir fluid with hydrocarbon components up to C30. Two pieces of equipment were used: a sapphire cell with a maximum pressure rating of 400 bar and a high pressure apparatus called Hercule with a maximum pressure of 1500 bar. For each fluid, the saturation pressure was measured. For various pressure levels below saturation, the coexisting liquid and gas phases were sampled at constant pressure, and subsequently analyzed by gas chromatography. In the gas injection study, sampling was repeated with different quantities of injection gas. Compared to a n-paraffin with the same number of carbon atoms, aromatic hydrocarbons appear to stay preferentially in the liquid phase, as do cycloalkanes to a lesser extent. The gaseous phase is slightly enriched in isoalkanes. These fractionation effects are less pronounced near the critical region. These phenomena have been modeled with a cubic equation of state combined with a group contribution mixing rule. L'étude du fractionnement des hydrocarbures légers entre les phases gazeuses et liquides intéresse plusieurs domaines dans le cadre de l'exploitation des gisements. En géochimie de réservoir l'évolution de la composition de la fraction légère peut

  16. Characterization of silane coated hollow sphere alumina-reinforced

    Indian Academy of Sciences (India)

    Silane coated hollow sphere alumina ceramic particles were moulded with ultra high molecular weight polyethylene (UHMWPE) to form a series of composites with alumina weight percent in the range from 15 to 50. The composites were prepared in a cylindrical mould using powder-processing technique. The composites ...

  17. Characterization of silane coated hollow sphere alumina-reinforced ...

    Indian Academy of Sciences (India)

    Silane coated hollow sphere alumina ceramic particles were moulded with ultra high molecular weight polyethylene (UHMWPE) to form a series of composites with alumina weight percent in the range from 15 to 50. The composites were prepared in a cylindrical mould using powder-processing technique. The composites ...

  18. Evaluation of gamma radiation effects on stationary phases using gas chromatografy

    International Nuclear Information System (INIS)

    Basso, M.A.; Collins, K.E.; Collins, C.H.


    The overall objetive of this project is a thorough study of the effect of gamma radiation on supported stationary phases used in packed-column gas chromatography. The phases studied were SP-2100 on Supelcoport and SE-30 on Chromsorb W. The fases were irradiated with cobalt-60 gamma rays to various doses and subsequently subjected to tests of extractability, termal stability and efficiency as a chromatographic column packing. Extraction tests indicate that low doses of radiation are sufficient to produce significant immobilization of these polymethylsilicones; that is, to produce chemical bonds between different polymer chains or between the stationary phase and the support. Thermal stability is also increased. The values calculated for the number of theoretical plates (n) and resolution (Rsub (s)) after analysis of four synthetic mixtures of organic compounds also increase, in most cases, indicating that the gamma irradiation has positively altered the behavior of these stationary phases. (author) [pt

  19. Effect of silane contamination on dentin bond strength. (United States)

    Chen, Liang; Hammond, Barry D; Alex, Gary; Suh, Byoung In


    Intraoral repair of porcelain or other silica-based ceramics typically requires the use of silane in the repair protocol. Some porcelain intraoral repairs also involve bonding to exposed or involved tooth tissues including dentin. A study is needed to evaluate whether the cross-contamination of dentin with silane affects bond strength to this tissue. The purpose of this in vitro study was to investigate the effect of silane cross-contamination on dentin bond strength. Flat surfaces of human dentin specimens were created, followed by wet polishing with 320-grit silicon carbide paper. The dentin specimens were divided into 4 groups: group SE (All-Bond Universal Adhesive used in self-etching mode); group SiSE (silane applied to dentin followed by All-Bond Universal Adhesive used in self-etching mode); group ER (All-Bond Universal Adhesive used in total-etch (etch-and-rinse) mode); and group ERSi (Etch and rinse and silane applied to dentin followed by All-Bond Universal Adhesive). The dentin specimens were treated with a universal adhesive (All-Bond Universal) and bonded with a composite resin, using an Ultradent jig mold. Shear bond strength (n=10) was measured after 24 hours of water storage at 37°C. After the shear bond strength test, the dentin sides of fractured specimens in each group were examined with a stereomicroscope at ×15 magnification to determine failure modes. Data were statistically analyzed by 2-way and a 1-way ANOVA followed by post hoc Tukey honest significant difference test (α=.05). Scanning electron microscopy examination was used to evaluate the dentin surface morphology before and after bonding. The shear bond strength of composite resin to dentin was not affected adversely when the dentin was contaminated with silane prior to using All-Bond Universal in the self-etch or total- etch (phosphoric acid) mode. SE, 30.3 ±3.8 MPa; SiSE, 32.9 ±3.9 MPa; ER, 34.9 ±3.1 MPa; ERSi: 35.2 ±4.9 MPa (P>.05) CONCLUSIONS: Under the conditions of this


    Energy Technology Data Exchange (ETDEWEB)

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


    In this chapter we review the spectroscopic data for actinide molecules and the reaction dynamics for atomic and molecular actinides that have been examined in the gas phase or in inert cryogenic matrices. The motivation for this type of investigation is that physical properties and reactions can be studied in the absence of external perturbations (gas phase) or under minimally perturbing conditions (cryogenic matrices). This information can be compared directly with the results from high-level theoretical models. The interplay between experiment and theory is critically important for advancing our understanding of actinide chemistry. For example, elucidation of the role of the 5f electrons in bonding and reactivity can only be achieved through the application of experimentally verified theoretical models. Theoretical calculations for the actinides are challenging due the large numbers of electrons that must be treated explicitly and the presence of strong relativistic effects. This topic has been reviewed in depth in Chapter 17 of this series. One of the goals of the experimental work described in this chapter has been to provide benchmark data that can be used to evaluate both empirical and ab initio theoretical models. While gas-phase data are the most suitable for comparison with theoretical calculations, there are technical difficulties entailed in generating workable densities of gas-phase actinide molecules that have limited the range of species that have been characterized. Many of the compounds of interest are refractory, and problems associated with the use of high temperature vapors have complicated measurements of spectra, ionization energies, and reactions. One approach that has proved to be especially valuable in overcoming this difficulty has been the use of pulsed laser ablation to generate plumes of vapor from refractory actinide-containing materials. The vapor is entrained in an inert gas, which can be used to cool the actinide species to room

  1. Chlorination of some eliphatic organic compounds in liquid and gas phase

    International Nuclear Information System (INIS)

    Hassan, A.A.


    The photochlorination of different organic compounds and the relative slectivities of different positions have been investigated in both gaseous and liquid phases at different temperatures. The results have shown that the relative selectivity generally decreased with increasing temperature and in the gas phase has a higher value. Polar solvents increase the selectivity relative to the chlorination of pure liquid phases. The differences in activation energy between two positions were much higher in the gas phases chlorination, relative to that in the liquid phase. It was also found that the functional groups have great influence on the rate of chlorine free radical attack on different positions, for example the electron withdrawing groups decreasing the selectivity on the first position, but the electron donating groups increase the selectivity on the first position, but the electron donating groups increase the selectivity on the first position. Furthermore it was found that the polar solvents, which stabilize the resonance between oxygen and carbon atoms, increases the selectivity on that position. 23 tabs.; 16 figs.; 50 refs

  2. Fluorometric method for the determination of gas-phase hydrogen peroxide (United States)

    Kok, Gregory L.; Lazrus, Allan L.


    The fluorometric gas-phase hydrogen peroxide procedure is based on the technique used by Lazrus et. al. for the determination of H2O2 in the liquid phase. The analytical method utilizes the reaction of H2O2 with horseradish peroxidase and p-hydroxphenylacetic acid (POPHA) to form the fluorescent dimer of POPHA. The analytical reaction responds stoichiometrically to both H2O2 and some organic hydroperoxides. To discriminate H2O2 from organic hydroperoxides, catalase is used to preferentially destroy H2O2. Using a dual-channel flow system the H2O2 concentration is determined by difference.

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

    International Nuclear Information System (INIS)

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


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

  4. Measurement of gas phase characteristics using new monofiber optical probes and real time signal processing

    International Nuclear Information System (INIS)

    Cartellier, A.


    Single optical or impedance phase detection probes are able to measure gas velocities provided that their sensitive length L is accurately known. In this paper, it is shown that L can be controlled during the manufacture of optical probes. Beside, for a probe geometry in the form of a cone + a cylinder + a cone, the corresponding rise time / velocity correlation becomes weakly sensitive to uncontrollable parameter such as the angle of impact on the interface. A real time signal processing performing phase detection as well as velocity measurements is described. Since its sensitivity to the operator inputs is less than the reproducibility of measurements, it is a fairly objective tool. Qualifications achieved in air/water flows with various optical probes demonstrate that the void fraction is detected with a relative error less than 10 %. For bubbly flows, the gas flux is accurate within ±10%, but this uncertainty increases when large bubbles are present in the flow. (author)

  5. Methods and apparatus for using gas and liquid phase cathodic depolarizers (United States)

    Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)


    The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

  6. ICR studies of some anionic gas phase reactions and FTICR software design

    International Nuclear Information System (INIS)

    Noest, A.J.


    This thesis consists of two parts. Part one (Chs. 1-5) reports experimental results from mostly drift-cell ICR studies of negative ion-molecule reactions; part two (Chs. 6-11) concerns the design of software for an FTICR instrument. The author discusses successively: 1. ion cyclotron resonance spectrometry; 2. the gas phase allyl anion; 3. the (M-H) and (M-H2) anions from acetone; 4. negative ion-molecule reactions of aliphatic nitrites studied by cyclotron resonance; 5. homoconjugation versus charge-dipole interaction effects in the stabilization of carbanions in the gas phase; 6. the Fourier Transform ICR method; 7. the FTICR-software; 8. an efficient adaptive matcher filter for fast transient signals; 9. reduction of spectral peak height errors by time-domain weighing; 10. Chirp excitation; 11. Compact data storage. The book concludes with a Dutch and English summary (G.J.P.)

  7. UV-Vis absorption spectra and electronic structure of merocyanines in the gas phase (United States)

    Ishchenko, Alexander A.; Kulinich, Andrii V.; Bondarev, Stanislav L.; Raichenok, Tamara F.


    Gas-phase absorption spectra of a merocyanine vinylogous series have been studied for the first time. In vapour, their long-wavelength absorption bands were found to be considerably shifted hypsochromically, broader, more symmetrical, less intense, and their vinylene shift much smaller than even in low-polarity n-hexane. This indicates that in the gas phase their electronic structure closely approaches the nonpolar polyene limiting structure. The TDDFT calculations of the long-wavelength electronic transitions in the studied merocyanines in vacuo demonstrated good-to-excellent correlation - depending on the functional used - with the obtained experimental data. For comparison, the solvent effects was accounted for using the polarizable continuum model (PCM) with n-hexane and ethanol as low-polarity and high-polarity media, and compared with the UV-Vis spectral data in these solvents. In this case, the discrepancy between theory and experiment was much greater, increasing at that with the polymethine chain length.

  8. Ultraslow isomerization in photoexcited gas-phase carbon cluster [Formula: see text]. (United States)

    Saha, K; Chandrasekaran, V; Heber, O; Iron, M A; Rappaport, M L; Zajfman, D


    Isomerization and carbon chemistry in the gas phase are key processes in many scientific studies. Here we report on the isomerization process from linear [Formula: see text] to its monocyclic isomer. [Formula: see text] ions were trapped in an electrostatic ion beam trap and then excited with a laser pulse of precise energy. The neutral products formed upon photoexcitation were measured as a function of time after the laser pulse. It was found using a statistical model that, although the system is excited above its isomerization barrier energy, the actual isomerization from linear to monocyclic conformation takes place on a very long time scale of up to hundreds of microseconds. This finding may indicate a general phenomenon that can affect the interstellar medium chemistry of large molecule formation as well as other gas phase processes.

  9. Theoretical investigation of the long-lived metastable AlO2+ dication in gas phase

    International Nuclear Information System (INIS)

    Sghaier, Onsi; Abdallah, Hassan H.; Abdullah, Hewa Y.; Jaidane, Nejm Eddine; Al Mogren, Muneerah Mogren; Hochlaf, Majdi


    Highlights: • Theoretical investigation of gas-phase molecular species AlO 2+ . • Spectroscopic parameters of this dication in its electronic ground and exited states. • Theoretical double ionization spectrum of AlO. - Abstract: We report the results of a detailed theoretical study of the electronic ground and excited states of the gas-phase doubly charged ion AlO 2+ using high-level ab initio computer calculations. Both standard and explicitly correlated methods were used to calculate their potential energy curves and spectroscopic parameters. These computations show that the ground state of AlO 2+ is X 2 Π. The internuclear equilibrium distance of AlO 2+ (X 2 Π) is computed 1.725 Å. We also deduced the adiabatic double ionization and charge stripping energies of AlO to be about 27.45 eV and 17.80 eV, respectively.

  10. Mass-independent oxygen isotopic partitioning during gas-phase SiO2 formation. (United States)

    Chakraborty, Subrata; Yanchulova, Petia; Thiemens, Mark H


    Meteorites contain a wide range of oxygen isotopic compositions that are interpreted as heterogeneity in solar nebula. The anomalous oxygen isotopic compositions of refractory mineral phases may reflect a chemical fractionation process in the nebula, but there are no experiments to demonstrate this isotope effect during particle formation through gas-phase reactions. We report experimental results of gas-to-particle conversion during oxidation of silicon monoxide that define a mass-independent line (slope one) in oxygen three-isotope space of (18)O/(16)O versus (17)O/(16)O. This mass-independent chemical reaction is a potentially initiating step in nebular meteorite formation, which would be capable of producing silicate reservoirs with anomalous oxygen isotopic compositions.

  11. Ab initio treatment of gas phase GeO{sup 2+} doubly charged ion

    Energy Technology Data Exchange (ETDEWEB)

    Mogren Al Mogren, M. [Chemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451 (Saudi Arabia); Ben Abdallah, D. [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications – LSAMA, Université de Tunis, Tunis (Tunisia); Department of General Studies, Riyadh Corporation of Technology, Technical and Vocational Training Corporation, PO Box 42826, Riyadh 11551 (Saudi Arabia); Hochlaf, M., E-mail: [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)


    Highlights: • Theoretical investigation of the novel gas-phase molecular species GeO{sup 2+}. • Spectroscopic parameters of this dication in its electronic ground and exited states. • Theoretical double ionization spectrum of GeO. - Abstract: Using multi reference configuration interaction methodology in connection with a large basis set, we show that GeO{sup 2+} is a metastable species either in the ground or in the electronically excited states. This confirms the observation of this dication in gas phase by mass spectrometry. In addition, we derived a set of accurate spectroscopic terms for GeO{sup 2+} bound states. At the MRCI/aug-cc-pV5Z level of theory, the adiabatic double ionization energy of GeO is computed to be ∼28.93 eV.

  12. Unusual hydroxyl migration in the fragmentation of β-alanine dication in the gas phase. (United States)

    Piekarski, Dariusz Grzegorz; Delaunay, Rudy; Maclot, Sylvain; Adoui, Lamri; Martín, Fernando; Alcamí, Manuel; Huber, Bernd A; Rousseau, Patrick; Domaracka, Alicja; Díaz-Tendero, Sergio


    We present a combined experimental and theoretical study of the fragmentation of doubly positively charged β-alanine molecules in the gas phase. The dissociation of the produced dicationic molecules, induced by low-energy ion collisions, is analysed by coincidence mass spectrometric techniques; the coupling with ab initio molecular dynamics simulations allows rationalisation of the experimental observations. The present strategy gives deeper insights into the chemical mechanisms of multiply charged amino acids in the gas phase. In the case of the β-alanine dication, in addition to the expected Coulomb explosion and hydrogen migration processes, we have found evidence of hydroxyl-group migration, which leads to unusual fragmentation products, such as hydroxymethyl cation, and is necessary to explain some of the observed dominant channels.

  13. Improved gas installations and services. Phase 1: Analysis project. Part report

    International Nuclear Information System (INIS)

    Nielsen, K.J.


    As Danish gas companies receive a large number of complaints related to the installation and operation of gas installations it was suggested that a course for personnel should be established in order to raise the standard of services and installation requirements. The first phase of the described project was to evaluate the quality of the gas installers' services so as to determine which aspects of installation and services should be emphasized during such a course. Interviews were carried out and questionnaires (illustrated within the document) sent out to installaters etc. Recommendations include that the level of information given to customers should be raised, also in relation to maintenance, and that installation should be improved. Analyses of the degree of customers' satisfaction, of the nature of the quality of services etc. expected, subjects for further training in this area and details of the training system are dealt with

  14. Phase diagram and universality of the Lennard-Jones gas-liquid system

    KAUST Repository

    Watanabe, Hiroshi


    The gas-liquid phase transition of the three-dimensional Lennard-Jones particles system is studied by molecular dynamics simulations. The gas and liquid densities in the coexisting state are determined with high accuracy. The critical point is determined by the block density analysis of the Binder parameter with the aid of the law of rectilinear diameter. From the critical behavior of the gas-liquid coexisting density, the critical exponent of the order parameter is estimated to be β = 0.3285(7). Surface tension is estimated from interface broadening behavior due to capillary waves. From the critical behavior of the surface tension, the critical exponent of the correlation length is estimated to be ν = 0.63(4). The obtained values of β and ν are consistent with those of the Ising universality class. © 2012 American Institute of Physics.

  15. Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane. (United States)

    Itami, Kenichiro; Mitsudo, Koichi; Nishino, Akira; Yoshida, Jun-ichi


    Metal-catalyzed hydrosilylation of alkenes and alkynes using dimethyl(pyridyl)silane is described. The hydrosilylation of alkenes using dimethyl(2-pyridyl)silane (2-PyMe(2)SiH) proceeded well in the presence of a catalytic amount of RhCl(PPh(3))(3) with virtually complete regioselectivity. By taking advantage of the phase tag property of the 2-PyMe(2)Si group, hydrosilylation products were isolated in greater than 95% purity by simple acid-base extraction. Strategic catalyst recovery was also demonstrated. The hydrosilylation of alkynes using 2-PyMe(2)SiH proceeded with a Pt(CH(2)=CHSiMe(2))(2)O/P(t-Bu)(3) catalyst to give alkenyldimethyl(2-pyridyl)silanes in good yield with high regioselectivity. A reactivity comparison of 2-PyMe(2)SiH with other related hydrosilanes (3-PyMe(2)SiH, 4-PyMe(2)SiH, and PhMe(2)SiH) was also performed. In the rhodium-catalyzed reaction, the reactivity order of hydrosilane was 2-PyMe(2)SiH > 3-PyMe(2)SiH, 4-PyMe(2)SiH, PhMe(2)SiH, indicating a huge rate acceleration with 2-PyMe(2)SiH. In the platinum-catalyzed reaction, the reactivity order of hydrosilane was PhMe(2)SiH, 3-PyMe(2)SiH > 4-PyMe(2)SiH > 2-PyMe(2)SiH, indicating a rate deceleration with 2-PyMe(2)SiH and 4-PyMe(2)SiH. It seems that these reactivity differences stem primarily from the governance of two different mechanisms (Chalk-Harrod and modified Chalk-Harrod mechanisms). From the observed reactivity order, coordination and electronic effects of dimethyl(pyridyl)silanes have been implicated.

  16. Plasma processes for producing silanes and derivatives thereof (United States)

    Laine, Richard M; Massey, Dean Richard; Peterson, Peter Young


    The invention is generally related to process for generating one or more molecules having the formula Si.sub.xH.sub.y, Si.sub.xD.sub.y, Si.sub.xH.sub.yD.sub.z, and mixtures thereof, where x,y and z are integers .gtoreq.1, H is hydrogen and D is deuterium, such as silane, comprising the steps of: providing a silicon containing material, wherein the silicon containing material includes at least 20 weight percent silicon atoms based on the total weight of the silicon containing material; generating a plasma capable of vaporizing a silicon atom, sputtering a silicon atom, or both using a plasma generating device; and contacting the plasma to the silicon containing material in a chamber having an atmosphere that includes at least about 0.5 mole percent hydrogen atoms and/or deuterium atoms based on the total moles of atoms in the atmosphere; so that a molecule having the formula Si.sub.xH.sub.y; (e.g., silane) is generated. The process preferably includes a step of removing one or more impurities from the Si.sub.xH.sub.y (e.g., the silane) to form a clean Si.sub.xH.sub.y, Si.sub.xD.sub.y, Si.sub.xH.sub.yD.sub.z (e.g., silane). The process may also include a step of reacting the Si.sub.xH.sub.y, Si.sub.xD.sub.y, Si.sub.xH.sub.yD.sub.z (e.g., the silane) to produce a high purity silicon containing material such as electronic grade metallic silicon, photovoltaic grade metallic silicon, or both.

  17. Conformational Study of DNA Sugars: from the Gas Phase to Solution (United States)

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


    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.

  18. Gas Phase Transport, Adsorption and Surface Diffusion in Porous Glass Membrane

    Czech Academy of Sciences Publication Activity Database

    Yang, J.; Čermáková, Jiřina; Uchytil, Petr; Hamel, Ch.; Seidel-Morgenstern, A.


    Roč. 104, 2-4 (2005), s. 344-351 ISSN 0920-5861. [International Conference on Catalysis in Membrane Reactors /6./. Lahnstein, 06.07.2004-09.07.2004] R&D Projects: GA AV ČR(CZ) IAA4072402 Institutional research plan: CEZ:AV0Z40720504 Keywords : gas phase transport * vycor glass * adsorption Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.365, year: 2005

  19. Method and apparatus for selective capture of gas phase analytes using metal .beta.-diketonate polymers (United States)

    Harvey, Scott D [Kennewick, WA


    A process and sensor device are disclosed that employ metal .beta.-diketonate polymers to selectively capture gas-phase explosives and weaponized chemical agents in a sampling area or volume. The metal .beta.-diketonate polymers can be applied to surfaces in various analytical formats for detection of: improvised explosive devices, unexploded ordinance, munitions hidden in cargo holds, explosives, and chemical weapons in public areas.

  20. Unexpected epoxide formation in the gas-phase photooxidation of isoprene

    DEFF Research Database (Denmark)

    Paulot, Fabien; Crounse, John D; Kjaergaard, Henrik G


      Emissions of nonmethane hydrocarbon compounds to the atmosphere from the biosphere exceed those from anthropogenic activity. Isoprene, a five-carbon diene, contributes more than 40% of these emissions. Once emitted to the atmosphere, isoprene is rapidly oxidized by the hydroxyl radical OH. We...... per year-of these epoxides to the atmosphere. The discovery of these highly soluble epoxides provides a missing link tying the gas-phase degradation of isoprene to the observed formation of organic aerosols....

  1. Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth Reactions (United States)


    photodissociation reactions of ketene, methylamine, formic acid , methyl ethyl ketone, acetone and NO3. For instance, for NO3, a totally photodissociation reactions of ketene, methylamine, formic acid , methyl ethyl ketone, acetone and NO3. For instance, for NO3, a totally unknown...THEORETICAL STUDIES OF GAS PHASE ELEMENTARY AND CARBON NANOSTRUCTURE GROWTH REACTIONS KEIJI MOROKUMA EMORY UNIVERSITY 09/19/2013 Final Report

  2. Position for determining gas-phase volatile organic compound concentrations in transuranic waste containers. Revision 2

    International Nuclear Information System (INIS)

    Connolly, M.J.; Liekhus, K.J.


    In the conditional no-migration determination (NMD) for the test phase of the Waste Isolation Pilot Plant (WIPP), the US Environmental Protection Agency (EPA) imposed certain conditions on the US Department of Energy (DOE) regarding gas phase volatile organic compound (VOC) concentrations in the void space of transuranic (TRU) waste containers. Specifically, the EPA required the DOE to ensure that each waste container has no layer of confinement that contains flammable mixtures of gases or mixtures of gases that could become flammable when mixed with air. The EPA also required that sampling of the headspace of waste containers outside inner layers of confinement be representative of the entire void space of the container. The EPA stated that all layers of confinement in a container would have to be sampled until DOE can demonstrate to the EPA that sampling of all layers is either unnecessary or can be safely reduced. A test program was conducted at the Idaho National Engineering and Environmental Laboratory (INEEL) to demonstrate that the gas phase VOC concentration in the void space of each layer of confinement in vented drums can be estimated from measured drum headspace using a theoretical transport model and that sampling of each layer of confinement is unnecessary. This report summarizes the studies performed in the INEEL test program and extends them for the purpose of developing a methodology for determining gas phase VOC concentrations in both vented and unvented TRU waste containers. The methodology specifies conditions under which waste drum headspace gases can be said to be representative of drum gases as a whole and describes a method for predicting drum concentrations in situations where the headspace concentration is not representative. The methodology addresses the approach for determining the drum VOC gas content for two purposes: operational period drum handling and operational period no-migration calculations

  3. Radical Generation from the Gas-Phase Activation of Ionized Lipid Ozonides (United States)

    Ellis, Shane R.; Pham, Huong T.; in het Panhuis, Marc; Trevitt, Adam J.; Mitchell, Todd W.; Blanksby, Stephen J.


    Reaction products from the ozonolysis of unsaturated lipids at gas-liquid interfaces have the potential to significantly influence the chemical and physical properties of organic aerosols in the atmosphere. In this study, the gas-phase dissociation behavior of lipid secondary ozonides is investigated using ion-trap mass spectrometry. Secondary ozonides were formed by reaction between a thin film of unsaturated lipids (fatty acid methyl esters or phospholipids) with ozone before being transferred to the gas phase as [M + Na]+ ions by electrospray ionization. Activation of the ionized ozonides was performed by either energetic collisions with helium buffer-gas or laser photolysis, with both processes yielding similar product distributions. Products arising from the decomposition of the ozonides were characterized by their mass-to-charge ratio and subsequent ion-molecule reactions. Product assignments were rationalized as arising from initial homolysis of the ozonide oxygen-oxygen bond with subsequent decomposition of the nascent biradical intermediate. In addition to classic aldehyde and carbonyl oxide-type fragments, carbon-centered radicals were identified with a number of decomposition pathways that indicated facile unimolecular radical migration. These findings reveal that photoactivation of secondary ozonides formed by the reaction of aerosol-bound lipids with tropospheric ozone may initiate radical-mediated chemistry within the particle resulting in surface modification.

  4. Liquid and gas phase NMR spectra of 13CH313CHO acetaldehyde (United States)

    Makulski, Włodzimierz; Wikieł, Agata J.


    The gas phase NMR experiments perform a vital role in establishing the magnetic shielding and spin-spin coupling constants which are free from intermolecular interactions, equivalent to the parameter of isolated molecules. This work is concerned with an acetaldehyde molecule. Small amounts of acetaldehyde 13CH313CHO in gaseous matrices of CO2 and Xe were studied using high-precision 1H and 13C NMR measurements. Results were extrapolated to the zero-density limit permitting the determinations of the 1H and 13C absolute nuclear magnetic shielding of an isolated acetaldehyde molecule. The difference between the experimental and recent theoretical DFT results is discussed. Several samples of 13CH313CHO dissolved in popular organic and inorganic solvents were also investigated. Gas-to-solution shifts show the influence of the association process when acetaldehyde is transferred from gas to liquid state. Several spin-spin coupling constants in the gas phase and in different solvents were precisely measured.

  5. Functionalized silica aerogels for gas-phase purification, sensing, and catalysis: A review

    Energy Technology Data Exchange (ETDEWEB)

    Amonette, James E.; Matyáš, Josef


    Silica aerogels have a rich history and a unique, fascinating gas-phase chemistry that has lent them to many diverse applications. This review starts with a brief discussion of the fundamental issues driving the movement of gases in silica aerogels and then proceeds to provide an overview of the work that has been done with respect to the purification of gases, sensing of individual gases, and uses of silica aerogels as catalysts for gas-phase reactions. Salient features of the research behind these different applications are presented, and, where appropriate, critical aspects that affect the practical use of the aerogels are noted. Specific sections under the gas-purification category focus on the removal of airborne nanoparticles, carbon dioxide, volatile organic compounds, sulfur gases and radioactive iodine from gas streams. The use of silica aerogels as sensors for humidity, oxygen, hydrocarbons, volatile acids and bases, various non-ammoniacal nitrogen gases, and viral particles is discussed. With respect to catalysis, the demonstrated use of silica aerogels as supports for oxidation, Fischer-Tropsch, alkane isomerization, and hydrogenation reactions is reviewed, along with a section on untested catalytic formulations involving silica aerogels. A short section focuses on recent developments in thermomolecular Knudsen compressor pumps using silica aerogel membranes. The review continues with an overview of the production methods, locations of manufacturing facilities globally, and a brief discussion of the economics before concluding with a few remarks about the present and future trends revealed by the work presented.

  6. Source reconciliation of atmospheric gas-phase and particle-phase pollutants during a severe photochemical smog episode. (United States)

    Schauer, James J; Fraser, Matthew P; Cass, Glen R; Simoneit, Bernd R T


    A comprehensive organic compound-based receptor model is developed that can simultaneously apportion the source contributions to atmospheric gas-phase organic compounds, semivolatile organic compounds, fine particle organic compounds, and fine particle mass. The model is applied to ambient data collected at four sites in the south coast region of California during a severe summertime photochemical smog episode, where the model determines the direct primary contributions to atmospheric pollutants from 11 distinct air pollution source types. The 11 sources included in the model are gasoline-powered motor vehicle exhaust, diesel engine exhaust, whole gasoline vapors, gasoline headspace vapors, organic solvent vapors, whole diesel fuel, paved road dust, tire wear debris, meat cooking exhaust, natural gas leakage, and vegetative detritus. Gasoline engine exhaust plus whole gasoline vapors are the predominant sources of volatile organic gases, while gasoline and diesel engine exhaust plus diesel fuel vapors dominate the emissions of semivolatile organic compounds from these sources during the episode studied at all four air monitoring sites. The atmospheric fine particle organic compound mass was composed of noticeable contributions from gasoline-powered motor vehicle exhaust, diesel engine exhaust, meat cooking, and paved road dust with smaller but quantifiable contributions from vegetative detritus and tire wear debris. In addition, secondary organic aerosol, which is formed from the low-vapor pressure products of gas-phase chemical reactions, is found to be a major source of fine particle organic compound mass under the severe photochemical smog conditions studied here. The concentrations of secondary organic aerosol calculated in the present study are compared with previous fine particle source apportionment results for less intense photochemical smog conditions. It is shown that estimated secondary organic aerosol concentrations correlate fairly well with the

  7. Modelling of stratified gas-liquid two-phase flow in horizontal circular pipes

    International Nuclear Information System (INIS)

    Sampaio, P.A.B. de; Faccini, J.L.H.; Su, J.


    This paper reports numerical and experimental investigation of stratified gas-liquid two-phase flow in horizontal circular pipes. The Reynolds average Navier-Stokes equations (RANS) with κ ω model development stratified gas-liquid two-phase flow are solved by using the finite element methods. A smooth interface surface is assumed without considered the effects of the interfacial waves. The continuity of the shear stress across the interface is enforced with the continuity of the velocity being automatically satisfied by the variational formulation. For it is given position and interface and longitudinal pressure gradient, an inner iteration loop runs to solve nonlinear equations the Newton-Raphson scheme is used to solve the transcendental equations by an outer iteration to determinate the interface position in a 5.2 mm ID circular pipe was measured experimentally by the ultrasonic ultra pulse-echo technique. The numeral were also compared with results in 21 mm ID circular pipe report by Masala (2004). The good agreement between the numerical and experimental results indicates that κ ω model can be applied for the numerical simulation of stratified gas-liquid two phase flow. (author)

  8. Temperature dependence of gas-phase polycyclic aromatic hydrocarbon and organochlorine pesticide concentrations in Chicago air (United States)

    Sofuoglu, Aysun; Odabasi, Mustafa; Tasdemir, Yucel; Khalili, Nasrin R.; Holsen, Thomas M.

    The temperature dependence of gas-phase atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides measured in Chicago, IL between June and October 1995 were investigated using plots of the natural logarithm of partial pressures (ln P) vs. reciprocal mean temperatures (1/ T). For the eight lowest molecular weight PAHs, temperature dependence was statistically significant (at the 95% confidence level) and temperature accounted for 23-49% of the variability in gas-phase concentrations. The relatively higher slopes for most of the PAHs suggested that volatilization from local sources and short-range transport influenced their concentrations. For pesticides, temperature dependence was statistically significant for DDD and for trans-nonachlor (at the 95% and 90% confidence levels), and was not statistically significant for the other five compounds (2-18% of the variability in their gas-phase concentrations). The relatively lower slopes for individual pesticides suggested that they have mostly non-urban and distant sources. Results of back trajectory analyses suggested that the region, southwest of Chicago, might be an important local or regional source sector for PAHs and organochlorine pesticides. No statistically significant relationship was observed between wind speed and PAH or pesticide concentrations. None of the variables (temperature, wind speed, wind direction, local and regional sources) could fully explain the variation in their concentrations measured in Chicago, therefore, this variation can be attributed to the combined effect of those factors.

  9. Thermodynamic analysis of fuels in gas phase: ethanol, gasoline and ethanol - gasoline predicted by DFT method. (United States)

    Neto, A F G; Lopes, F S; Carvalho, E V; Huda, M N; Neto, A M J C; Machado, N T


    This paper presents a theoretical study using density functional theory to calculate thermodynamics properties of major molecules compounds at gas phase of fuels like gasoline, ethanol, and gasoline-ethanol mixture in thermal equilibrium on temperature range up to 1500 K. We simulated a composition of gasoline mixture with ethanol for a thorough study of thermal energy, enthalpy, Gibbs free energy, entropy, heat capacity at constant pressure with respect to temperature in order to study the influence caused by ethanol as an additive to gasoline. We used semi-empirical computational methods as well in order to know the efficiency of other methods to simulate fuels through this methodology. In addition, the ethanol influence through the changes in percentage fractions of chemical energy released in combustion reaction and the variations on thermal properties for autoignition temperatures of fuels was analyzed. We verified how ethanol reduces the chemical energy released by gasoline combustion and how at low temperatures the gas phase fuels in thermal equilibrium have similar thermodynamic behavior. Theoretical results were compared with experimental data, when available, and showed agreement. Graphical Abstract Thermodynamic analysis of fuels in gas phase.

  10. The influence of non condensible gas on two phase critical flow

    International Nuclear Information System (INIS)

    Celata, G.P.; Cumo, M.; D'Annibale, F.; Farello, G.E.


    With reference to Loss-of-Coolant Accidents in Pressurized Water Reactors and in the frame of the wide scientific landscape of blowdown experiments aiming to the improvement of two-phase critical flows knowledge, it is of interest the analysis of non condensible gas influence on the critical flow (radiolytic gases,metal-water reactions products etc.). The present paper deals with an experiment referring to two-phase steam-water critical flows from long tubes, in which known air flowrates are injected in the stagnation region. The aim of the experiment is to detect the influence of non-condensible gas on the two-phase critical flow behaviour (critical mass flow rate, pressure and temperature profiles along the discharge channel etc.) as well as to individuate the limit, in terms of air concentration, beyond which the critical flow is affected by the presence of the gas. The employed test section is a vertical, circular duct channel with an inner diameter of 4.6 mm and a length of 1500 mm (L/D = 325). Results of initially subcooled liquid experiments (together with some data of satured liquid discharges), up to 15 bars are reported with the analysis of non-condensible effects in the different stagnation conditions

  11. Improved machine learning method for analysis of gas phase chemistry of peptides

    Directory of Open Access Journals (Sweden)

    Ahn Natalie


    Full Text Available Abstract Background Accurate peptide identification is important to high-throughput proteomics analyses that use mass spectrometry. Search programs compare fragmentation spectra (MS/MS of peptides from complex digests with theoretically derived spectra from a database of protein sequences. Improved discrimination is achieved with theoretical spectra that are based on simulating gas phase chemistry of the peptides, but the limited understanding of those processes affects the accuracy of predictions from theoretical spectra. Results We employed a robust data mining strategy using new feature annotation functions of MAE software, which revealed under-prediction of the frequency of occurrence in fragmentation of the second peptide bond. We applied methods of exploratory data analysis to pre-process the information in the MS/MS spectra, including data normalization and attribute selection, to reduce the attributes to a smaller, less correlated set for machine learning studies. We then compared our rule building machine learning program, DataSqueezer, with commonly used association rules and decision tree algorithms. All used machine learning algorithms produced similar results that were consistent with expected properties for a second gas phase mechanism at the second peptide bond. Conclusion The results provide compelling evidence that we have identified underlying chemical properties in the data that suggest the existence of an additional gas phase mechanism for the second peptide bond. Thus, the methods described in this study provide a valuable approach for analyses of this kind in the future.

  12. New quantum chemical computations of formamide deuteration support gas-phase formation of this prebiotic molecule (United States)

    Skouteris, D.; Vazart, F.; Ceccarelli, C.; Balucani, N.; Puzzarini, C.; Barone, V.


    Based on recent work, formamide might be a potentially very important molecule in the emergence of terrestrial life. Although detected in the interstellar medium for decades, its formation route is still debated, whether in the gas phase or on the dust grain surfaces. Molecular deuteration has proven to be, in other cases, an efficient way to identify how a molecule is synthesized. For formamide, new published observations towards the IRAS16293-2422 B hot corino show that its three deuterated forms have all the same deuteration ratio, 2-5 per cent and that this is a factor of 3-8 smaller than that measured for H2CO towards the IRAS16293-2422 protostar. Following a previous work on the gas-phase formamide formation via the reaction NH2 + H2CO → HCONH2 + H, we present here new calculations of the rate coefficients for the production of monodeuterated formamide through the same reaction, starting from monodeuterated NH2 or H2CO. Some misconceptions regarding our previous treatment of the reaction are also cleared up. The results of the new computations show that, at the 100 K temperature of the hot corino, the rate of deuteration of the three forms is the same, within 20 per cent. On the contrary, the reaction between non-deuterated species proceeds three times faster than that with deuterated ones. These results confirm that a gas-phase route for the formation of formamide is perfectly in agreement with the available observations.

  13. The Gas-Phase Formation of Methyl Formate in Hot Molecular Cores (United States)

    Horn, Anne; Møllendal, Harald; Sekiguchi, Osamu; Uggerud, Einar; Roberts, Helen; Herbst, Eric; Viggiano, A. A.; Fridgen, Travis D.


    Methyl formate, HCOOCH3, is a well-known interstellar molecule prominent in the spectra of hot molecular cores. The current view of its formation is that it occurs in the gas phase from precursor methanol, which is synthesized on the surfaces of grain mantles during a previous colder era and evaporates while temperatures increase during the process of high-mass star formation. The specific reaction sequence thought to form methyl formate, the ion-molecule reaction between protonated methanol and formaldehyde followed by dissociative recombination of the protonated ion [HCO(H)OCH3]+, has not been studied in detail in the laboratory. We present here the results of both a quantum chemical study of the ion-molecule reaction between [CH3OH2]+ and H2CO as well as new experimental work on the system. In addition, we report theoretical and experimental studies for a variety of other possible gas-phase reactions leading to ion precursors of methyl formate. The studied chemical processes leading to methyl formate are included in a chemical model of hot cores. Our results show that none of these gas-phase processes produces enough methyl formate to explain its observed abundance.

  14. Enantiomer-Selective Photo-Induced Reaction of Protonated Tryptophan with Disaccharides in the Gas Phase (United States)

    Doan, Thuc N.; Fujihara, Akimasa


    In order to investigate chemical evolution in interstellar molecular clouds, enantiomer-selective photo-induced chemical reactions between an amino acid and disaccharides in the gas phase were examined using a tandem mass spectrometer containing an electrospray ionization source and a cold ion trap. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of protonated tryptophan (Trp) enantiomers with disaccharides consisting of two d-glucose units, such as d-maltose or d-cellobiose, were obtained by photoexcitation of the indole ring of Trp. NH2CHCOOH loss via cleavage of the Cα-Cβ bond in Trp induced by hydrogen atom transfer from the NH3 + group of a protonated Trp was observed in a noncovalent heterochiral H+( l-Trp)( d-maltose) complex. In contrast, a photo-induced chemical reaction forming the product ion with m/z 282 occurs in homochiral H+( d-Trp)( d-maltose). For d-cellobiose, both NH2CHCOOH elimination and the m/z 282 product ion were observed, and no enantiomer-selective phenomena occurred. The m/z 282 product ion indicates that the photo-induced C-glycosylation, which links d-glucose residues to the indole moiety of Trp via a C-C bond, can occur in cold gas-phase noncovalent complexes, and its enantiomer-selectivity depends on the structure of the disaccharide.

  15. Revision of the gas-phase acidity scale below 300 kcal mol(-1). (United States)

    Leito, Ivo; Raamat, Elin; Kütt, Agnes; Saame, Jaan; Kipper, Karin; Koppel, Ilmar A; Koppel, Ivar; Zhang, Min; Mishima, Masaaki; Yagupolskii, Lev M; Garlyauskayte, Romute Yu; Filatov, Andrey A


    The gas-phase acidity (GA) scale from (CF(3)CO)(2)NH to (C(2)F(5)SO(2))(2)NH--about a 24 kcal mol(-1) range of gas-phase acidities--was reexamined using the Fourier transform ion cyclotron resonance equilibrium measurement approach. Some additions and modifications to the standard methodology of GA measurements were introduced (estimation of partial pressures from mass spectra of the compounds, instead of the pressure gauge readings and use of long reaction times) to achieve higher reliability. Gas-phase acidities of 18 compounds were determined for the first time. The results reveal a contraction of the previously published values in this part of the scale. In particular, the GA values of (CF(3)SO(2))(2)NH and (C(2)F(5)SO(2))(2)NH (important components of lithium ion battery electrolytes and ionic liquids) were revised toward stronger acidities from 291.8 kcal mol(-1) to 286.5 kcal mol(-1) and from 289.4 kcal mol(-1) to 283.7 kcal mol(-1) (i.e., by 5.3 and 5.7 kcal mol(-1)), respectively. Experimental and computational evidence is presented in support of the current results.

  16. Systematic Search for Chemical Reactions in Gas Phase Contributing to Methanol Formation in Interstellar Space. (United States)

    Gamez-Garcia, Victoria G; Galano, Annia


    A massive search for chemical routes leading to methanol formation in gas phase has been conducted using computational chemistry, at the CBS-QB3 level of theory. The calculations were performed at five different temperatures (100, 80, 50, 20, and 10 K) and at three pressures (0.1, 0.01, and 0.001 atm) for each temperature. The search was focused on identifying reactions with the necessary features to be viable in the interstellar medium (ISM). A searching strategy was applied to that purpose, which allowed to reduce an initial set of 678 possible reactions to a subset of 11 chemical routes that are recommended, for the first time, as potential candidates for contributing to methanol formation in the gas phase of the ISM. They are all barrier-less, and thus they are expected to take place at collision rates. Hopefully, including these reactions in the currently available models, for the gas-phase methanol formation in the ISM, would help improving the predicted fractional abundance of this molecule in dark clouds. Further investigations, especially those dealing with grain chemistry and electronic excited states, would be crucial to get a complete picture of the methanol formation in the ISM.

  17. Probing the regional distribution of pulmonary gas exchange through single-breath gas- and dissolved-phase 129Xe MR imaging. (United States)

    Kaushik, S Sivaram; Freeman, Matthew S; Cleveland, Zackary I; Davies, John; Stiles, Jane; Virgincar, Rohan S; Robertson, Scott H; He, Mu; Kelly, Kevin T; Foster, W Michael; McAdams, H Page; Driehuys, Bastiaan


    Although some central aspects of pulmonary function (ventilation and perfusion) are known to be heterogeneous, the distribution of diffusive gas exchange remains poorly characterized. A solution is offered by hyperpolarized 129Xe magnetic resonance (MR) imaging, because this gas can be separately detected in the lung's air spaces and dissolved in its tissues. Early dissolved-phase 129Xe images exhibited intensity gradients that favored the dependent lung. To quantitatively corroborate this finding, we developed an interleaved, three-dimensional radial sequence to image the gaseous and dissolved 129Xe distributions in the same breath. These images were normalized and divided to calculate "129Xe gas-transfer" maps. We hypothesized that, for healthy volunteers, 129Xe gas-transfer maps would retain the previously observed posture-dependent gradients. This was tested in nine subjects: when the subjects were supine, 129Xe gas transfer exhibited a posterior-anterior gradient of -2.00 ± 0.74%/cm; when the subjects were prone, the gradient reversed to 1.94 ± 1.14%/cm (P gas-transfer maps also exhibited significant heterogeneity, as measured by the coefficient of variation, that correlated with subject total lung capacity (r = 0.77, P = 0.015). Gas-transfer intensity varied nonmonotonically with slice position and increased in slices proximal to the main pulmonary arteries. Despite substantial heterogeneity, the mean gas transfer for all subjects was 1.00 ± 0.01 while supine and 1.01 ± 0.01 while prone (P = 0.25), indicating good "matching" between gas- and dissolved-phase distributions. This study demonstrates that single-breath gas- and dissolved-phase 129Xe MR imaging yields 129Xe gas-transfer maps that are sensitive to altered gas exchange caused by differences in lung inflation and posture.

  18. Fluidized bed silicon deposition from silane (United States)

    Hsu, George (Inventor); Levin, Harry (Inventor); Hogle, Richard A. (Inventor); Praturi, Ananda (Inventor); Lutwack, Ralph (Inventor)


    A process and apparatus for thermally decomposing silicon containing gas for deposition on fluidized nucleating silicon seed particles is disclosed. Silicon seed particles are produced in a secondary fluidized reactor by thermal decomposition of a silicon containing gas. The thermally produced silicon seed particles are then introduced into a primary fluidized bed reactor to form a fludized bed. Silicon containing gas is introduced into the primary reactor where it is thermally decomposed and deposited on the fluidized silicon seed particles. Silicon seed particles having the desired amount of thermally decomposed silicon product thereon are removed from the primary fluidized reactor as ultra pure silicon product. An apparatus for carrying out this process is also disclosed.

  19. Silane adhesion mechanism in dental applications and surface treatments: A review. (United States)

    Matinlinna, Jukka Pekka; Lung, Christie Ying Kei; Tsoi, James Kit Hon


    To give a current review of silane adhesion chemistry, applications of silane coupling agents and related surface pretreatment methods in contemporary dentistry. Silane coupling agents are adhesion promoters to chemically unify dissimilar materials used in dentistry. Silanes are very effective in adhesion promotion between resin composites and silica-based or silica-coated indirect restorative materials. It is generally accepted that for non-silica-based restorations, surface pretreatment is a mandatory preliminary step to increase the silica content and then, with help of silane, improve resin bonding. This review discusses the silane-based adhesion chemistry, silane applications in dentistry, surface pretreatment methods, and presents the recent development of silane coupling agents. A silane coupling agent is considered a reliable, good adhesion promoter to silica-based (or silica-coated) indirect restorations. Surface pre-treatment steps, e.g., acid etching for porcelain and tribo-chemical silica-coating for metal alloys, is used before silanization to attain strong, durable bonding of the substrate to resin composite. In clinical practice, however, the main problem of resin bonding using silanes and other coupling agents is the weakening of the bond (degradation) in the wet oral environment over time. A silane coupling agent is a justified and popular adhesion promoter (adhesive primer) used in dentistry. The commercial available silane coupling agents can fulfil the requirements in clinical practice for durable bonding. Development of new silane coupling agents, their optimization, and surface treatment methods are in progress to address the long term resin bond durability and are highly important. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  20. Ecological and climatic consequences of phase instability of gas hydrates on the ocean bed (United States)

    Balanyuk, I.; Dmitrievsky, A.; Akivis, T.; Chaikina, O.


    energy and gas that leads to explosion. Methane is the main natural source for power engineering specialists. It is transported by pipelines, and gas hydrate is dangerous in this case too. It can block the gas pipeline system forming the so-called "trombus" of "thermal ice". After that the pipes have to be opened. The mess of this strange ice discovered melts immediately releasing methane and water vapor. The trombus formation can be prevented by the temperature increase or the pressure decrease. Both methods are very uncomfortable under the conditions the pipelines work. The better method is thorough drying up of the gas because gas hydrate obviously cannot be formed without water. Gas hydrates attract attention not only as a fuel and chemical stuff but in relation to a serious anxiety of strong ecological and climatic problems that can occur as a result of methane release to the atmosphere due to both gas hydrate deposits development and minor changes in thermodynamic conditions in the vicinity of a threshold of gas hydrate phase stability. One of the most probable causes is the global warming of the Earth due to the hothouse effect because the specific absorption of the Earth heat radiation by methane (radiation effectivity) is 21 times higher than its absorption by carbonic gas. Analysis of the air trapped by polar ice show that contemporary increase of methane concentration in the atmosphere is unexampled for the last 160 thousands of years. The sources of this increase are not clear. Observer and latent methane bursts during natural gas hydrates decomposition can be considered as a probable source. Amount of methane hided in natural gas hydrates is 3000 times higher its amount in the atmosphere. Release of this hothouse potential would have terrible consequences for the humanity. The warming can cause further gas hydrates decomposition and released methane will cause the following warming. Thus, self-accelerating process can start. The most vulnerable for the

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

    International Nuclear Information System (INIS)

    Howard, J A; Walsh, P A


    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

  2. Evaluation of Gas Phase Dispersion in Flotation under Predetermined Hydrodynamic Conditions (United States)

    Młynarczykowska, Anna; Oleksik, Konrad; Tupek-Murowany, Klaudia


    Results of various investigations shows the relationship between the flotation parameters and gas distribution in a flotation cell. The size of gas bubbles is a random variable with a specific distribution. The analysis of this distribution is useful to make mathematical description of the flotation process. The flotation process depends on many variable factors. These are mainly occurrences like collision of single particle with gas bubble, adhesion of particle to the surface of bubble and detachment process. These factors are characterized by randomness. Because of that it is only possible to talk about the probability of occurence of one of these events which directly affects the speed of the process, thus a constant speed of flotation process. Probability of the bubble-particle collision in the flotation chamber with mechanical pulp agitation depends on the surface tension of the solution, air consumption, degree of pul aeration, energy dissipation and average feed particle size. Appropriate identification and description of the parameters of the dispersion of gas bubbles helps to complete the analysis of the flotation process in a specific physicochemical conditions and hydrodynamic for any raw material. The article presents the results of measurements and analysis of the gas phase dispersion by the size distribution of air bubbles in a flotation chamber under fixed hydrodynamic conditions. The tests were carried out in the Laboratory of Instrumental Methods in Department of Environmental Engineering and Mineral Processing, Faculty of Mining and Geoengineerin, AGH Univeristy of Science and Technology in Krakow.

  3. Evaluation of Gas Phase Dispersion in Flotation under Predetermined Hydrodynamic Conditions

    Directory of Open Access Journals (Sweden)

    Młynarczykowska Anna


    Full Text Available Results of various investigations shows the relationship between the flotation parameters and gas distribution in a flotation cell. The size of gas bubbles is a random variable with a specific distribution. The analysis of this distribution is useful to make mathematical description of the flotation process. The flotation process depends on many variable factors. These are mainly occurrences like collision of single particle with gas bubble, adhesion of particle to the surface of bubble and detachment process. These factors are characterized by randomness. Because of that it is only possible to talk about the probability of occurence of one of these events which directly affects the speed of the process, thus a constant speed of flotation process. Probability of the bubble-particle collision in the flotation chamber with mechanical pulp agitation depends on the surface tension of the solution, air consumption, degree of pul aeration, energy dissipation and average feed particle size. Appropriate identification and description of the parameters of the dispersion of gas bubbles helps to complete the analysis of the flotation process in a specific physicochemical conditions and hydrodynamic for any raw material. The article presents the results of measurements and analysis of the gas phase dispersion by the size distribution of air bubbles in a flotation chamber under fixed hydrodynamic conditions. The tests were carried out in the Laboratory of Instrumental Methods in Department of Environmental Engineering and Mineral Processing, Faculty of Mining and Geoengineerin, AGH Univeristy of Science and Technology in Krakow.

  4. Determination of gas & liquid two-phase flow regime transitions in wellbore annulus by virtual mass force coefficient when gas cut (United States)

    Qu, Junbo; Yan, Tie; Sun, Xiaofeng; Chen, Ye; Pan, Yi


    With the development of drilling technology to deeper stratum, overflowing especially gas cut occurs frequently, and then flow regime in wellbore annulus is from the original drilling fluid single-phase flow into gas & liquid two-phase flow. By using averaged two-fluid model equations and the basic principle of fluid mechanics to establish the continuity equations and momentum conservation equations of gas phase & liquid phase respectively. Relationship between pressure and density of gas & liquid was introduced to obtain hyperbolic equation, and get the expression of the dimensionless eigenvalue of the equation by using the characteristic line method, and analyze wellbore flow regime to get the critical gas content under different virtual mass force coefficients. Results show that the range of equation eigenvalues is getting smaller and smaller with the increase of gas content. When gas content reaches the critical point, the dimensionless eigenvalue of equation has no real solution, and the wellbore flow regime changed from bubble flow to bomb flow. When virtual mass force coefficients are 0.50, 0.60, 0.70 and 0.80 respectively, the critical gas contents are 0.32, 0.34, 0.37 and 0.39 respectively. The higher the coefficient of virtual mass force, the higher gas content in wellbore corresponding to the critical point of transition flow regime, which is in good agreement with previous experimental results. Therefore, it is possible to determine whether there is a real solution of the dimensionless eigenvalue of equation by virtual mass force coefficient and wellbore gas content, from which we can obtain the critical condition of wellbore flow regime transformation. It can provide theoretical support for the accurate judgment of the annular flow regime.

  5. Is it biologically relevant to measure the structures of small peptides in the gas-phase? (United States)

    Barran, Perdita E.; Polfer, Nick C.; Campopiano, Dominic J.; Clarke, David J.; Langridge-Smith, Patrick R. R.; Langley, Ross J.; Govan, John R. W.; Maxwell, Alison; Dorin, Julia R.; Millar, Robert P.; Bowers, Michael T.


    Recent developments in sample introduction of biologically relevant molecules have heralded a new era for gas-phase methods of structural determination. One of the biggest challenges is to relate gas-phase structures, often measured in the absence of water and counter ions, with in vivo biologically active structures. An advantage of gas-phase based techniques is that a given peptide can be analysed in a variety of different forms, for example, as a function of charge state, or with additional water molecules. Molecular modelling can provide insight into experimental findings and help elucidate the differences between structural forms. Combining experiment and theory provides a thorough interrogation of candidate conformations. Here two important naturally occurring peptide systems have been examined in detail and results are assessed in terms of their biological significance. The first of these is gonadotropin-releasing hormone (GnRH), a decapeptide which is the central regulator of the reproductive system in vertebrates. We have examined several naturally occurring variants of this peptide using Ion Mobility Mass Spectrometry and Electron Capture Dissociation (ECD) in conjunction with Fourier Transform Ion Cyclotron Mass Spectrometry (FT-ICR-MS). Candidate conformations are modelled using the AMBER force field. Single amino acid changes, for example Gly6 --> Ala6, or Ala6 --> D-Ala6, have observable effects on the gas phase structure of GnRH. It has been shown that evolutionary primary sequence variations are key to the biological activity of GnRH, and it is thought that this is due to different binding affinities at target receptors. This work provides strong evidence that this activity is structurally based. The second system examined is the relationship between the quaternary structure and activity of two novel [beta]-defensins. FT-ICR mass spectrometry has been employed to characterize di-sulphide bridging and dissociation based experiments utilised to

  6. Absolute standard hydrogen electrode potential measured by reduction of aqueous nanodrops in the gas phase. (United States)

    Donald, William A; Leib, Ryan D; O'Brien, Jeremy T; Bush, Matthew F; Williams, Evan R


    In solution, half-cell potentials are measured relative to those of other half cells, thereby establishing a ladder of thermochemical values that are referenced to the standard hydrogen electrode (SHE), which is arbitrarily assigned a value of exactly 0 V. Although there has been considerable interest in, and efforts toward, establishing an absolute electrochemical half-cell potential in solution, there is no general consensus regarding the best approach to obtain this value. Here, ion-electron recombination energies resulting from electron capture by gas-phase nanodrops containing individual [M(NH3)6]3+, M = Ru, Co, Os, Cr, and Ir, and Cu2+ ions are obtained from the number of water molecules that are lost from the reduced precursors. These experimental data combined with nanodrop solvation energies estimated from Born theory and solution-phase entropies estimated from limited experimental data provide absolute reduction energies for these redox couples in bulk aqueous solution. A key advantage of this approach is that solvent effects well past two solvent shells, that are difficult to model accurately, are included in these experimental measurements. By evaluating these data relative to known solution-phase reduction potentials, an absolute value for the SHE of 4.2 +/- 0.4 V versus a free electron is obtained. Although not achieved here, the uncertainty of this method could potentially be reduced to below 0.1 V, making this an attractive method for establishing an absolute electrochemical scale that bridges solution and gas-phase redox chemistry.

  7. Bacteria and fungi inactivation by photocatalysis under UVA irradiation: liquid and gas phase. (United States)

    Rodrigues-Silva, Caio; Miranda, Sandra M; Lopes, Filipe V S; Silva, Mário; Dezotti, Márcia; Silva, Adrián M T; Faria, Joaquim L; Boaventura, Rui A R; Vilar, Vítor J P; Pinto, Eugénia


    In the last decade, environmental risks associated with wastewater treatment plants (WWTPs) have become a concern in the scientific community due to the absence of specific legislation governing the occupational exposure limits (OEL) for microorganisms present in indoor air. Thus, it is necessary to develop techniques to effectively inactivate microorganisms present in the air of WWTPs facilities. In the present work, ultraviolet light A radiation was used as inactivation tool. The microbial population was not visibly reduced in the bioaerosol by ultraviolet light A (UVA) photolysis. The UVA photocatalytic process for the inactivation of microorganisms (bacteria and fungi, ATCC strains and isolates from indoor air samples of a WWTP) using titanium dioxide (TiO 2 P25) and zinc oxide (ZnO) was tested in both liquid-phase and airborne conditions. In the slurry conditions at liquid phase, P25 showed a better performance in inactivation. For this reason, gas-phase assays were performed in a tubular photoreactor packed with cellulose acetate monolithic structures coated with P25. The survival rate of microorganisms under study decreased with the catalyst load and the UVA exposure time. Inactivation of fungi was slower than resistant bacteria, followed by Gram-positive bacteria and Gram-negative bacteria. Graphical abstract Inactivation of fungi and bacteria in gas phase by photocatalitic process performed in a tubular photoreactor packed with cellulose acetate monolith structures coated with TiO 2 .

  8. Probing Vitamine C, Aspirin and Paracetamol in the Gas Phase: High Resolution Rotational Studies (United States)

    Mata, S.; Cabezas, C.; Varela, M.; Pena, I.; Nino, A.; López, J. C.; Alonso, J. L.; Grabow, J.-U.


    A solid sample of Vitamin C (m.p. 190°C) vaporized by laser ablation has been investigated in gas phase and characterized through their rotational spectra. Two spectroscopy techniques has been used to obtain the spectra: a new design of broadband chirped pulse Fourier transform microwave spectroscopy with in-phase/quadrature-phase-modulation passage-acquired-coherence technique (IMPACT) and conventional laser ablation molecular beam Fourier transform microwave spectroscopy (LA-MB-FTMW). Up to now, two low-energy conformer have been observed and their rotational constants determined. Ab initio calculations at the MP2/6-311++G (d,p) level of theory predicted rotational constants which helped us to identify these conformers unequivocally. Among the molecules to benefit from the LA-MB-FTMW technique there are common important drugs never observed in the gas phase through rotational spectroscopy. We present here the results on acetyl salicylic acid and acetaminophen (m.p. 136°C), commonly known as aspirin and paracetamol respectively. We have observed two stable conformers of aspirin and two for paracetamol. The internal rotation barrier of the methyl group in aspirin has been determined for both conformers from the analysis of the A-E splittings due to the coupling of internal and overall rotation. J. L. Alonso, C. Pérez, M. E. Sanz, J. C. López, S. Blanco, Phys. Chem. Chem. Phys. 11,617-627 (2009)and references therein

  9. Nucleation and dissociation of nano-particles in gas phase; Nucleation et evaporation de nanoparticules en phase gazeuse

    Energy Technology Data Exchange (ETDEWEB)

    Feiden, P


    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{sub n} and heterogeneous Na{sub n}X particles (X = (NaOH){sub 2} or (Na{sub 2}O){sub 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{sup +}(NaOH){sub p} et Na{sup +}(NaF){sub 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{sup +} Na{sup +} (NaOH){sub p} clusters shows a competition between the fission into two single charged fragments and the unimolecular evaporation of a neutral fragment. (author)

  10. The closed spiracle phase of discontinuous gas exchange predicts diving duration in the grasshopper Paracinema tricolor. (United States)

    Gudowska, Agnieszka; Boardman, Leigh; Terblanche, John S


    The discontinuous gas exchange (DGE) pattern of respiration shown by many arthropods includes periods of spiracle closure (C-phase) and is largely thought to serve as a physiological adaptation to restrict water loss in terrestrial environments. One major challenge to this hypothesis is to explain the presence of DGE in insects in moist environments. Here, we show a novel ecological correlate of the C-phase, namely, diving behaviour in mesic Paracinema tricolor grasshoppers. Notably, maximal dive duration is positively correlated with C-phase length, even after accounting for mass scaling and absolute metabolic rate. Here, we propose that an additional advantage of DGE may be conferred by allowing the tracheal system to act as a sealed underwater oxygen reservoir. Spiracle closure may facilitate underwater submersion, which, in turn, may contribute to predator avoidance, the survival of accidental immersion or periodic flooding and the exploitation of underwater resources. © 2016. Published by The Company of Biologists Ltd.

  11. Gas-phase simulated moving bed: Propane/propylene separation on 13X zeolite. (United States)

    Martins, Vanessa F D; Ribeiro, Ana M; Plaza, Marta G; Santos, João C; Loureiro, José M; Ferreira, Alexandre F P; Rodrigues, Alírio E


    In the last years several studies were carried out in order to separate gas mixtures by SMB technology; however, this technology has never been implemented on an industrial scale. In the present work, a gas phase SMB bench unit was built and tested for the separation of propane and propylene mixtures, using 13X zeolite extrudates as adsorbent and isobutane as desorbent. Three experiments were performed to separate propane/propylene by gas phase SMB in the bench scale unit with a 4-2-2 configuration, i.e., open loop circuit by suppressing section IV (desorbent regeneration followed by a recycle). Consequently, all the experiments were conducted using an external supply of pure isobutane as desorbent. Parameters such as switching time, extract and raffinate stream flow rates were changed to improve the efficiency of the process. Experimental results have shown that it is feasible to separate propylene from propane by gas phase SMB at a bench scale and that this process is a potential candidate to replace the conventional technologies for the propane/propylene separation. The performance parameters obtained are very promising for future development of this technology, since propylene was obtained in the extract stream with a purity of 99.93%, a recovery of 99.51%, and a productivity of [Formula: see text] . Propane was obtained in the raffinate stream with a purity of 98.10%, a recovery of 99.73% and a productivity of [Formula: see text] . The success of the above mentioned bench scale tests is a big step for the future implementation of this technology in a larger scale. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Contact line motion in confined liquid–gas systems: Slip versus phase transition

    KAUST Repository

    Xu, Xinpeng


    In two-phase flows, the interface intervening between the two fluid phases intersects the solid wall at the contact line. A classical problem in continuum fluid mechanics is the incompatibility between the moving contact line and the no-slip boundary condition, as the latter leads to a nonintegrable stress singularity. Recently, various diffuse-interface models have been proposed to explain the contact line motion using mechanisms missing from the sharp-interface treatments in fluid mechanics. In one-component two-phase (liquid–gas) systems, the contact line can move through the mass transport across the interface while in two-component (binary) fluids, the contact line can move through diffusive transport across the interface. While these mechanisms alone suffice to remove the stress singularity, the role of fluid slip at solid surface needs to be taken into account as well. In this paper, we apply the diffuse-interface modeling to the study of contact line motion in one-component liquid–gas systems, with the fluid slip fully taken into account. The dynamic van der Waals theory has been presented for one-component fluids, capable of describing the two-phase hydrodynamics involving the liquid–gas transition [A. Onuki, Phys. Rev. E 75, 036304 (2007)]. This theory assumes the local equilibrium condition at the solid surface for density and also the no-slip boundary condition for velocity. We use its hydrodynamicequations to describe the continuum hydrodynamics in the bulk region and derive the more general boundary conditions by introducing additional dissipative processes at the fluid–solid interface. The positive definiteness of entropy production rate is the guiding principle of our derivation. Numerical simulations based on a finite-difference algorithm have been carried out to investigate the dynamic effects of the newly derived boundary conditions, showing that the contact line can move through both phase transition and slip, with their relative

  13. Shock attenuation in two-phase (gas-liquid) jets for inertial fusion applications (United States)

    Lascar, Celine C.

    Z-Pinch IFE (Inertial Fusion Energy) reactor designs will likely utilize high yield targets (˜ 3 GJ) at low repetition rates (˜ 0.1 Hz). Appropriately arranged thick liquid jets can adequately protect the cavity walls from the target X-rays, ions, and neutrons. However, the shock waves and mechanical loadings produced by rapid heating and evaporation of incompressible liquid jets may be challenging to accommodate within a small reactor cavity. This investigation examines the possibility of using two-phase compressible (liquid/gas) jets to protect the cavity walls in high yield IFE systems, thereby mitigating the mechanical consequences of rapid energy deposition within the jets. Two-phase, free, vertical jets with different cross sections (planar, circular, and annular) were examined over wide ranges of liquid velocities and void fractions. The void fraction and bubble size distributions within the jets were measured; correlations to predict variations of the slip ratio and the Sauter mean diameter were developed. An exploding wire system was used to generate a shock wave at the center of the annular jets. Attenuation of the shock by the surrounding single- or two-phase medium was measured. The results show that stable coherent jets can be established and steadily maintained over a wide range of inlet void fractions and liquid velocities, and that significant attenuation in shock strength can be attained with relatively modest void fractions (˜ 1%); the compressible two-phase jets effectively convert and dissipate mechanical energy into thermal energy within the gas bubbles. The experimental characteristics of single- and two-phase jets were compared against predictions of a state-of-art CFD code (FLUENTRTM ). The data obtained in this investigation will allow reactor system designers to predict the behavior of single- and two-phase jets and quantify their effectiveness in mitigating the consequences of shock waves on the cavity walls in high yield IFE systems.

  14. The phase equilibria of multicomponent gas hydrate in methanol/ethylene glycol solution based formation water

    International Nuclear Information System (INIS)

    Xu, Shurui; Fan, Shuanshi; Yao, Haiyuan; Wang, Yanhong; Lang, Xuemei; Lv, Pingping; Fang, Songtian


    Highlights: • The equilibrium data in THI solution based formation water is first investigated. • The 0.55 mass fraction concentration of EG 0.55 mass fraction fills the vacancy of this area. • The testing pressure range from 4.22 MPa to 34.72 MPa was rare in published data. - Abstract: In this paper, the three-phase coexistence points are generated for multicomponent gas hydrate in methanol (MeOH) solution for (0.05, 0.10, 0.15, and 0.35) mass fraction and ethylene glycol (EG) solution for (0.05, 0.10, 0.15, 0.35, 0.40 and 0.55) mass fraction. The phase equilibrium curves of different system were obtained by an isochoric pressure-search method on high pressure apparatus. The phase equilibrium regions of multicomponent gas hydrate were measured using the same composition of natural gas distributed in the South China Sea. And the different concentration solutions were prepared based formation water. The experimental data were measured in a wide range temperature from 267.74 to 298.53 K and a wide range pressure from 4.22 MPa to 34.72 MPa. The results showed that the hydrate phase equilibrium curves shifted to the inhibition region in accordance with the increased inhibitor concentration. In addition, the equilibrium temperature would decrease about 2.7 K when the concentration of MeOH increased 0.05 mass fraction. Besides, the suppression temperature was 1.25 K with the 0.05 mass fraction increase of EG concentration in the range of 0.05 mass fraction to 0.15 mass fraction. While in high EG concentration region, the suppression temperature was 3.3 K with the same increase of EG concentration (0.05 mass fraction).

  15. Aspects of silane coupling agents and surface conditioning in dentistry: an overview. (United States)

    Lung, Christie Ying Kei; Matinlinna, Jukka Pekka


    To give an overview of aspects of silane coupling agents and surface conditioning in dentistry. Currently, silane coupling agents are used as adhesion promoters. Silanes are effective in enhancing adhesion between resin composite and silica-based ceramics. They do not bond effectively to non-silica based dental restorative materials. Surface conditioning of non-silica based ceramics with silica coating improves the bonding. This current overview will focus on the silane coupling agents: their properties, limitations in adhesion promotion and the clinical problems with the use of silanes. It will also focus on the current surface conditioning methods as well as new surface conditioning techniques to enhance the bonding through conventional silanization approaches. Several surface conditioning methods are being used clinically to enhance the adhesion of resin composites to non-silica based restorative materials. Other approaches are under investigation. The clinical problem of using silanes in adhesion promotion is the bond degradation over time in oral environment. The current silane coupling agents are not ideal. The current silane coupling agents can fulfill the minimum requirements in clinical practice to enhance the bonding of resin composite to dental restorative materials. Developments of novel surface conditioning methods and silane coupling agents are required to address the bond durability problem. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  16. ART CCIM Phase II-A Off-Gas System Evaluation Test Plan

    Energy Technology Data Exchange (ETDEWEB)

    Nick Soelberg; Jay Roach


    This test plan defines testing to be performed using the Idaho National Laboratory (INL) engineering-scale cold crucible induction melter (CCIM) test system for Phase II-A of the Advanced Remediation Technologies (ART) CCIM Project. The multi-phase ART-CCIM Project is developing a conceptual design for replacing the joule-heated melter (JHM) used to treat high level waste (HLW) in the Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS) with a cold crucible induction melter. The INL CCIM test system includes all feed, melter off-gas control, and process control subsystems needed for fully integrated operation and testing. Testing will include operation of the melter system while feeding a non-radioactive slurry mixture prepared to simulate the same type of waste feed presently being processed in the DWPF. Process monitoring and sample collection and analysis will be used to characterize the off-gas composition and properties, and to show the fate of feed constituents, to provide data that shows how the CCIM retrofit conceptual design can operate with the existing DWPF off-gas control system.

  17. Aromatic substitution in the gas phase. Alkylation of arenes by gaseous C4H9+ cations

    International Nuclear Information System (INIS)

    Cacace, F.; Ciranni, G.; Giacomello, P.


    Butyl cations, obtained in the dilute gas state from the radiolysis of butane in the pressure range from 70 to 750 torr, have been allowed to react with benzene, toluene, and their mixtures or with trace amounts of o-xylene in the gaseous system. The gas-phase butylation yields invariably sec-butylarenes, remarkably free of isomeric byproducts, namely n- and tert-butylarenes. Other alkylation experiments, where gaseous butyl cations from the reaction of butane with radiolytically formed H 3 + ions were used as reagent, confirmed the exclusive formation of sec-butylarenes. The butylation process displays the positional and substrate selectivity and the dependence of orientation on the pressure of the system, typical of other gas-phase ionic substitutions. At high pressures, orth-para orientation predominates in the sec-butylation of toluene, with a ortho:meta:para ratio of 43:30:27 at 715 torr. As the pressure is reduced, a gradual shift in favor of the thermodynamically most stable meta-substituted arenium ion is observed, leading to a ortho:meta:para ratio of 31:48:21 at 70 torr

  18. Biofiltration of mixtures of gas-phase styrene and acetone with the fungus Sporothrix variecibatus

    Energy Technology Data Exchange (ETDEWEB)

    Rene, Eldon R.; Spackova, Radka; Veiga, Maria C. [University of La Coruna, Dpt. of Chemical Engineering, Campus da Zapateira, Rua da Fraga, 10, 15008 La Coruna (Spain); Kennes, Christian, E-mail: [University of La Coruna, Dpt. of Chemical Engineering, Campus da Zapateira, Rua da Fraga, 10, 15008 La Coruna (Spain)


    The biodegradation performance of a biofilter, inoculated with the fungus Sporothrix variecibatus, to treat gas-phase styrene and acetone mixtures under steady-state and transient conditions was evaluated. Experiments were carried out by varying the gas-flow rates (0.05-0.4 m{sup 3} h{sup -1}), leading to empty bed residence times as low as 17.1 s, and by changing the concentrations of gas-phase styrene (0.01-6.3 g m{sup -3}) and acetone (0.01-8.9 g m{sup -3}). The total elimination capacities were as high as 360 g m{sup -3} h{sup -1}, with nearly 97.5% removal of styrene and 75.6% for acetone. The biodegradation of acetone was inhibited by the presence of styrene, while styrene removal was affected only slightly by the presence of acetone. During transient-state experiments, increasing the overall pollutant load by almost 3-fold, i.e., from 220 to 600 g m{sup -3} h{sup -1}, resulted in a sudden drop of removal efficiency (>90-70%), but still high elimination capacities were maintained. Periodic microscopic observations revealed that the originally inoculated Sporothrix sp. remained present in the reactor and actively dominant in the biofilm.

  19. Gas-Phase Photolysis of Pyruvic Acid: The Effect of Pressure on Reaction Rates and Products. (United States)

    Reed Harris, Allison E; Doussin, Jean-Francois; Carpenter, Barry K; Vaida, Veronica


    In this work, we investigate the impact of pressure and oxygen on the kinetics of and products from the gas-phase photolysis of pyruvic acid. The results reveal a decrease in the photolysis quantum yield as pressure of air or nitrogen is increased, a trend not yet documented in the literature. A Stern-Volmer analysis demonstrates this effect is due to deactivation of the singlet state of pyruvic acid when the photolysis is performed in nitrogen, and from quenching of both the singlet and triplet state in air. Consistent with previous studies, acetaldehyde and CO 2 are observed as the major products; however, other products, most notably acetic acid, are also identified in this work. The yield of acetic acid increases with increasing pressure of buffer gas, an effect that is amplified by the presence of oxygen. At least two mechanisms are necessary to explain the acetic acid, including one that requires reaction of photolysis intermediates with O 2 . These findings extend the fundamental understanding of the gas-phase photochemistry of pyruvic acid, highlighting the importance of pressure on the photolysis quantum yields and products.


    Directory of Open Access Journals (Sweden)

    J. W. Tröger


    Full Text Available The use of oxy-fuel combustion processes is of large interest for several industrial fields applications since it offers the advantages of low NOx emissions in combination with high combustion temperatures even without additional preheating. For optimization of such processеs a detailed understanding based on precise experimental data is necessary. So far there is still a lack of precise experimental data achieved with high spatial and temporal resolution from industrial relevant turbulent oxy-fuel combustion processes. Beside species concentration information the gas phase temperature is of utmost importance for an improved understanding of the basic chemical reactions and the pollutant formation. The coherent anti-Stokes Raman spectroscopy (CARS technique is a very well suited laser based tool for a non-intrusive investigation of such turbulent high temperature combustion processes. In this work we analysed an industrial 400 kW oxy-fuel burner with the help of O2 based vibrational CARS system which is integrated in an industrial relevant test furnace. The burner is fed with pure oxygen and natural gas at an equivalence ratio of =0.9. At one downstream position temporal and spatial resolved temperatures were measured along a 600 mm line. Additional air sucked in from the environment seems to influence the gas phase temperature significantly.

  1. Bond strength between fiber posts and composite resin core: influence of temperature on silane coupling agents. (United States)

    Novais, Veridiana Resende; Simamotos Júnior, Paulo Cézar; Rontani, Regina Maria Puppin; Correr-Sobrinho, Lourenço; Soares, Carlos José


    This study evaluated the effect of air drying temperature and different silane coupling agents on the bond strength between glass fiber posts and composite resin core. The post surface was cleaned with alcohol and treated with different silane coupling agents, being three prehydrolyzed silanes [Silano (Angelus), Prosil (FGM), RelyX Ceramic Primer (3M ESPE)] and one two-component silane [Silane Coupling Agent (Dentsply)]. Two post-silanization air drying temperatures, 23ºC and 60ºC, were applied. A cylindrical plastic matrix was placed around the silanized post and filled with composite resin. Each bonded post provided 7 slices for push-out testing. Each slice was loaded to failure under compression at a cross-head speed of 0.5 mm/min. Data were analyzed by two-way ANOVA and Scott-Knott tests (α=0.05). Dunnett's test was used to compare the mean of the control group with that of each experimental group. Scanning electron microscopy (SEM) was used to evaluate the interface of the fractured slices. For the 23ºC air drying temperature, the use of RelyX Ceramic Primer resulted in significantly lower bond strength than the other silane coupling agents, while the bond strength with Silane Coupling Agent was the highest of all groups. Only with Silane Coupling Agent, the bond strength for the 23ºC air drying temperature was significantly higher than that for 60ºC air drying. In conclusion, the use of warm air drying after silane application produced no increase in the bond strength between the fiber-reinforced composite post and the composite core. The two-component silane produced higher bond strength than all prehydrolyzed silanes when it was used with air drying at room temperature.

  2. Coupled LBM-DEM Three-phase Simulation on Gas Flux Seeping from Marine Sediment (United States)

    Kano, Y.; Sato, T.


    One of the main issues of the geological storage of CO2 under the seabed is a risk of CO2 leakage. Once CO2seeps into the ocean, it rises in water column dissolving into seawater, which results in the acidification of seawater and/or returning to the air. Its behaviour significantly depends on flow rate and bubble size (Kano et al., 2009; Dewar et al., 2013). As for porous media, bubble size is generally predicted through simple force balance based on flow rate, surface tension and channel size which is estimated by porosity and grain size. However, in shallow marine sediments, grains could be mobilised and displaced by buoyant gas flow, which causes distinctive phenomena such as blow-out or formation of gas flow conduit. As a result, effective gas flux into seawater can be intermissive, and/or concentrated in narrow area (QICS, 2012; Kawada, 2013). Bubble size is also affected by these phenomena. To predict effective gas flux and bubble size into seawater, three-phase behaviour of gas-water-sediment grains should be revealed. In this presentation, we will report the results of gas-liquid-solid three-phase simulations and their comparisons with experimental and observation data. Size of solid particles is based on grain size composing marine sediments at some CCS project sites. Fluid-particle interactions are solved using the lattice Boltzmann method (LBM), while the particle-particle interactions are treated by coupling with the Discrete Element method (DEM). References: Dewar, M., Wei, W., McNeil, D., Chen, B., 2013. Small-scale modelling of the physiochemical impacts of CO2leaked from sub-seabed reservoirs or pipelines within the North Sea and surrounding waters. Marine Pollution Bulletin 73(2), 504-515. Kano, Y., Sato, T., Kita, J., Hirabayashi, S., Tabeta, S., 2009. Model prediction on the rise of pCO2 in uniform flows by leakage of CO2purposefully stored under the seabed. Int. J. Greenhouse Gas Control, Vol. 3(5), 617-625. Kawada, R. 2014. A study on the

  3. Hydrodynamic characteristics of a two-phase gas-liquid flow upward through a fixed bed of spherical particles

    Directory of Open Access Journals (Sweden)



    Full Text Available The influence of an electrochemically generated gas phase on the hydrodynamic characteristics of a three-phase system has been examined. The two-phase fluid, (gas-liquid, in which the liquid phase is the continuous one, flows through a packed bed with glass spheres. The influence of the liquid velocity was examined, as well as the gas velocity and particle diameter on the pressure drop through the fixed bed. It was found that with increasing liquid velocity (wl = 0.0162–0.03 m/s, the relative pressure drop decreases through the fixed bed. With increasing current density, the pressure drop increases, since greater gas quantities stay behind in the fixed bed. Besides, it was found that with decreasing diameter of the glass particles, the relative pressure drop also decreases. The relationship betweeen the experimentally obtained friction factor and the Reynolds number was established.

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

    National Research Council Canada - National Science Library

    Onishi, Yoshimoto; Yamada, Ken


    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...

  5. Velocity field measurement in gas-liquid metal two-phase flow with use of PIV and neutron radiography techniques

    International Nuclear Information System (INIS)

    Saito, Y.; Mishima, K.; Tobita, Y.; Suzuki, T.; Matsubayashi, M.


    Neutron radiography and PIV (Particle Image Velocimetry) techniques were applied to measurements of velocity field in gas-liquid metal two-phase flow. Visualization and measurements of two-phase flow were conducted using molten lead bismuth and nitrogen gas as working fluids and particles made of gold-cadmium (AuCd 3 ) inter-metallic alloy were employed as the tracer. Discrimination method between bubble and tracer images in two-phase flow was developed based on the σ-scaling method. Time-averaged liquid velocity fields, gas velocity fields and void profile were calculated from discriminated images, respectively. From these measurements, the basic characteristics of gas-liquid metal two-phase mixture were clarified. (author)

  6. Simultaneous measurements of formaldehyde and nitrous acid in dews and gas phase in the atmosphere of Santiago, Chile (United States)

    Rubio, María A.; Lissi, Eduardo; Villena, Guillermo; Elshorbany, Y. F.; Kleffmann, Jörg; Kurtenbach, Ralf; Wiesen, Peter


    The amounts of formaldehyde and nitrous acid (HONO) in gas phase and dews of Santiago de Chile were simultaneously measured. Formaldehyde concentrations values in the liquid phase (dews) correlate fairly well with those in the gaseous phase and are even higher than those expected from gas-dew equilibrium. On the other hand, nitrite concentrations in dews were considerably smaller (ca. 15 times) than those expected from the gas-phase concentrations. This under-saturation is attributed to diffusion limitations due to the relatively large HONO solubility. In agreement with this, under-saturation increases with the rate of dew formation and the pH of the collected waters, factors that should increase the rate of gas to liquid HONO transfer required to reach equilibrium.

  7. X-ray phase contrast with injected gas for tumor microangiography

    International Nuclear Information System (INIS)

    Lundström, U; Larsson, D H; Burvall, A; Hertz, H M; Westermark, U K; Henriksson, M Arsenian


    We show that the microvasculature of mouse tumors can be visualized using propagation-based phase-contrast x-ray imaging with gas as the contrast agent. The large density difference over the gas–tissue interface provides high contrast, allowing the imaging of small-diameter blood vessels with relatively short exposure times and low dose using a compact liquid-metal-jet x-ray source. The method investigated is applied to tumors (E1A/Ras-transformed mouse embryonic fibroblasts) grown in mouse ears, demonstrating sub-15-µm-diameter imaging of their blood vessels. The exposure time for a 2D projection image is a few seconds and a full tomographic 3D map takes some minutes. The method relies on the strength of the vasculature to withstand the gas pressure. Given that tumor vessels are known to be more fragile than normal vessels, we investigate the tolerance of the vasculature of 12 tumors to gas injection and find that a majority withstand 200 mbar pressures, enough to fill 12-µm-diameter vessels with gas. A comparison of the elasticity of tumorous and non-tumorous vessels supports the assumption of tumor vessels being more fragile. Finally, we conclude that the method has the potential to be extended to the imaging of 15 µm vessels in thick tissue, including mouse imaging, making it of interest for, e.g., angiogenesis research. (paper)

  8. Third-order gas-liquid phase transition and the nature of Andrews critical point

    Directory of Open Access Journals (Sweden)

    Tian Ma


    Full Text Available The main objective of this article is to study the nature of the Andrews critical point in the gas-liquid transition in a physical-vapor transport (PVT system. A dynamical model, consistent with the van der Waals equation near the Andrews critical point, is derived. With this model, we deduce two physical parameters, which interact exactly at the Andrews critical point, and which dictate the dynamic transition behavior near the Andrews critical point. In particular, it is shown that 1 the gas-liquid co-existence curve can be extended beyond the Andrews critical point, and 2 the transition is first order before the critical point, second-order at the critical point, and third order beyond the Andrews critical point. This clearly explains why it is hard to observe the gas-liquid phase transition beyond the Andrews critical point. Furthermore, the analysis leads naturally the introduction of a general asymmetry principle of fluctuations and the preferred transition mechanism for a thermodynamic system. The theoretical results derived in this article are in agreement with the experimental results obtained in (K. Nishikawa and T. Morita, Fluid behavior at supercritical states studied by small-angle X-ray scattering, Journal of Supercritical Fluid, 13 (1998, pp. 143-148. Also, the derived second-order transition at the critical point is consistent with the result obtained in (M. Fisher, Specific heat of a gas near the critical point, Physical Review, 136:6A (1964, pp. A1599-A1604.

  9. Rational surface silane modification for immobilizing glucose oxidase. (United States)

    Tian, Feibao; Guo, Yi; Lin, Feifei; Zhang, Yumei; Yuan, Qipeng; Liang, Hao


    Glucose oxidase (GOx) has many significant applications in biosensor and biocatalysis. In this study, we firstly quantitatively analyzed the binding efficiency of (3-aminopropyl) trimethoxysilane (APTES) modified onto the surface of GOx. It was found that the contents of the grafted silane did not significantly influence the relative activities and tertiary structures of all surface modified GOxs. Immobilization ratio and relative activity of all instances of APTES modified GOx increased, compared with those of native enzyme. However, good stability of immobilized GOx at extreme pH and high temperature could only be obtained when modified protein with low binding silane content. At pH 2.0, the immobilized GOx with low binding content showed a more than 600% activity, compared to the free enzyme. Therefore, rational surface modification would be beneficial to improving the activity and stability of immobilized enzyme as well as increasing loading amount. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Femtosecond time-resolved studies of coherent vibrational Raman scattering in large gas-phase molecules

    International Nuclear Information System (INIS)

    Hayden, C.C.; Chandler, D.W.


    Results are presented from femtosecond time-resolved coherent Raman experiments in which we excite and monitor vibrational coherence in gas-phase samples of benzene and 1,3,5-hexatriene. Different physical mechanisms for coherence decay are seen in these two molecules. In benzene, where the Raman polarizability is largely isotropic, the Q branch of the vibrational Raman spectrum is the primary feature excited. Molecules in different rotational states have different Q-branch transition frequencies due to vibration--rotation interaction. Thus, the macroscopic polarization that is observed in these experiments decays because it has many frequency components from molecules in different rotational states, and these frequency components go out of phase with each other. In 1,3,5-hexatriene, the Raman excitation produces molecules in a coherent superposition of rotational states, through (O, P, R, and S branch) transitions that are strong due to the large anisotropy of the Raman polarizability. The coherent superposition of rotational states corresponds to initially spatially oriented, vibrationally excited, molecules that are freely rotating. The rotation of molecules away from the initial orientation is primarily responsible for the coherence decay in this case. These experiments produce large (∼10% efficiency) Raman shifted signals with modest excitation pulse energies (10 μJ) demonstrating the feasibility of this approach for a variety of gas phase studies. copyright 1995 American Institute of Physics

  11. Land application uses for dry flue gas desulfurization by-products: Phase 3

    Energy Technology Data Exchange (ETDEWEB)

    Dick, W.; Bigham, J.; Forster, R.; Hitzhusen, F.; Lal, R.; Stehouwer, R.; Traina, S.; Wolfe, W.; Haefner, R.; Rowe, G.


    New flue gas desulfurization (FGD) scrubbing technologies create a dry, solid by-product material consisting of excess sorbent, reaction product that contains sulfate and sulfite, and coal fly ash. Generally, dry FGD by-products are treated as solid wastes and disposed in landfills. However, landfill sites are becoming scarce and tipping fees are constantly increasing. Provided the environmental impacts are socially and scientifically acceptable, beneficial uses via recycling can provide economic benefits to both the producer and the end user of the FGD. A study titled ''Land Application Uses for Dry Flue Gas Desulfurization By-Products'' was initiated in December, 1990 to develop and demonstrate large volume, beneficial uses of FGD by-products. Phase 1 and Phase 2 reports have been published by the Electric Power Research Institute (EPRI), Palo Alto, CA. Phase 3 objectives were to demonstrate, using field studies, the beneficial uses of FGD by-products (1) as an amendment material on agricultural lands and on abandoned surface coal mine land, (2) as an engineering material for soil stabilization and raid repair, and (3) to assess the environmental and economic impacts of such beneficial uses. Application of dry FGD by-product to three soils in place of agricultural limestone increased alfalfa (Medicago sativa L.) and corn (Zea may L.) yields. No detrimental effects on soil and plant quality were observed.

  12. Molecular dynamics simulation of gas-phase ozone reactions with sabinene and benzene. (United States)

    Ridgway, H F; Mohan, B; Cui, X; Chua, K J; Islam, M R


    Gas-phase reactions of ozone (O 3 ) with volatile organic compounds were investigated both by experiment and molecular simulations. From our experiments, it was found ozone readily reacts with VOC pure components and reduces it effectively. By introducing ozone intermittently, the reaction between VOC and ozone is markedly enhanced. In order to understand the relationship between intermediate reactions and end products, ozone reaction with benzene and alicyclic monoterpene sabinene were simulated via a novel hybrid quantum mechanical/molecular mechanics (QM/MM) algorithm that forced repeated bimolecular collisions. Molecular orbital (MO) rearrangements (manifested as bond dissociation or formation), resulting from the collisions, were computed by semi-empirical unrestricted Hartree-Fock methods (e.g., RM1). A minimum of 975 collisions between ozone and targeted organic species were performed to generate a distribution of reaction products. Results indicated that benzene and sabinene reacted with ozone to produce a range of stable products and intermediates, including carbocations, ring-scission products, as well as peroxy (HO 2 and HO 3 ) and hydroxyl (OH) radicals. Among the stable sabinene products observed included formaldehyde and sabina-ketone, which have been experimentally demonstrated in gas-phase ozonation reactions. Among the benzene ozonation products detected composed of oxygen mono-substituted aromatic C 6 H 5 O, which may undergo further transformation or rearrangement to phenol, benzene oxide or 2,4-cyclohexadienone; a phenomenon which has been experimentally observed in vapor-phase photocatalytic ozonation reactions. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. Applying ion-molecule reactions to studies of gas-phase protein structure

    Energy Technology Data Exchange (ETDEWEB)

    Ogorzalek Loo, R.R.; Loo, J.A.; Smith, R.D.


    Whether solution phase differences in protein higher order structure persist in the gas phase, is examined by means of proton transfer reactions on ions generated by electrospray ionization of different solution conformations. Ion-molecule reactions were carried out in the atmosphere-vacuum interface of a quadrupole mass spectrometer with a Y-shaped capillary inlet-reactor. An amine (dimethyl-, trimethyl-, or diethyl-) were delivered to one inlet arm. Reactivities of bovine cytochrome c ions sprayed from denatured and native solutions were determined; the ions generated shifted to about the same charge states. Addition of equal amounts of amine to ions generated from different solution conformations of bovine ubiquitin also yielded similar final charge states; however, the average charge state increased with temperature. Myoglobin and apomyoglobin also yielded similar final charge states. The results suggest that for the non-disulfide linked proteins, either there are not significant differences in gas phase higher order structure, or proton transfer reactions are not sensitive enough to detect higher order structural differences arising from noncovalent interactions. 2 refs, 2 figs. (DLC)

  14. Gas phase emitter effect of thulium within ceramic metal halide lamps in dependence on frequency

    Energy Technology Data Exchange (ETDEWEB)

    Ruhrmann, C.; Depta, M.; Bergner, A.; Hoebing, T.; Mentel, J.; Awakowicz, P. [Ruhr University Bochum, Electrical Engineering and Plasma Technology, D-44780 Bochum (Germany); Denissen, C.; Suijker, J. [Philips Lighting, Category Prof. Lamps, PO Box 80020, NL-5600JM Eindhoven (Netherlands)


    The gas phase emitter effect within ceramic metal halide (CMH) lamps reduces the effective work function of the electrode material and, therewith, the electrode temperature. An investigation of the gas phase emitter effect of thulium (Tm) within CMH lamps seeded with Tm iodide (TmI3) is carried out. For this purpose, phase resolved images of the arc attachment and measurements of the electrode temperature, Tm atom and ion densities are performed in dependence on operating frequency by pyrometry and optical emission spectroscopy. Additionally, the influence of a sodium iodide (NaI) admixture is studied. The emitter effect is generated by means of a monolayer of Tm atoms on the electrode surface generated by a Tm ion current within the cathodic phase. It overlaps onto the anodic phase at higher frequencies of some hundreds of hertz. The reason is the finite life time of the monolayer, which is determined by the adsorption energy of Tm on the tungsten surface. Due to the low electric field strength in front of the anode and the mass inertia, the emitter ions and atoms remain in front of the anode. They retard the decay of the monolayer and with it the increase of the work function. Moreover, a comparison of a lamp seeded with TmI3 and sodium iodide (NaI) with a lamp seeded only with TmI3 illustrates a slight reduction of the electrode tip temperature caused by a higher Tm saturation vapour pressure and a higher Tm amount within the lamp filling. The influence of Na appears to be quite low. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  15. Ethylene epoxidation promoted by methane gas-phase thermic oxidation. The influence of temperature

    International Nuclear Information System (INIS)

    Grigoryan, R.R.; Arsentiev, S.D.; Mantashyan, A.A.


    Ethylene epoxidation promoted by methane gas-phase thermic oxidation has been studied. The studies were carried out in a two-sectional reactor under flow conditions. The experiments were performed in different temperatures in the sections of the reactor. It was shown that when methane is oxidized in the first section of the reactor and ethylene is put into the second section, epoxidation of olefin occurs through the alkyl peroxy radical interaction with double bond of olefin. It was established that the dependences of epoxidation rate on temperatures in both first and second sections pass trough maximum. The substitution of methane with inert gas (argon) in the first section leads to significant decrease of rate of ethylene oxide accumulation in the second section

  16. Gas-Phase Photochemical Overall H2S Splitting by UV Light Irradiation. (United States)

    Baldovi, Herme G; Albero, Josep; Ferrer, Belen; Mateo, Diego; Alvaro, Mercedes; García, Hermenegildo


    Splitting of hydrogen sulfide is achieved to produce value-added chemicals. Upon irradiation at 254 nm in the gas phase and in the absence of catalysts or photocatalysts at near room temperature, H 2 S splits into stoichiometric amounts of H 2 and S with a quantum efficiency close to 50 %. No influence of the presence of CH 4 and CO 2 (typical components in natural gas and biogas in which H 2 S is an unwanted component) on the efficiency of overall H 2 S splitting was observed. A mechanism for the H 2 and S formation is proposed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Modeling of a three-phase reactor for bitumen-derived gas oil hydrotreating

    Directory of Open Access Journals (Sweden)

    R. Chacón


    Full Text Available A three-phase reactor model for describing the hydrotreating reactions of bitumen-derived gas oil was developed. The model incorporates the mass-transfer resistance at the gas-liquid and liquid-solid interfaces and a kinetic rate expression based on a Langmuir-Hinshelwood-type model. We derived three correlations for determining the solubility of hydrogen (H2, hydrogen sulfide (H2S and ammonia (NH3 in hydrocarbon mixtures and the calculation of the catalyst effectiveness factor was included. Experimental data taken from the literature were used to determine the kinetic parameters (stoichiometric coefficients, reaction orders, reaction rate and adsorption constants for hydrodesulfuration (HDS and hydrodenitrogenation (HDN and to validate the model under various operating conditions. Finally, we studied the effect of operating conditions such as pressure, temperature, LHSV, H2/feed ratio and the inhibiting effect of H2S on HDS and NH3 on HDN.

  18. Gas phase chemistry and removal of CH{sub 3}I during a severe accident

    Energy Technology Data Exchange (ETDEWEB)

    Karhu, A. [VTT. Energy, Esbo (Finland)


    The purpose of this literature review was to gather valuable information on the behavior of methyl iodide on the gas phase during a severe accident. The potential of transition metals, especially silver and copper, to remove organic iodides from the gas streams was also studied. Transition metals are one of the most interesting groups in the context of iodine mitigation. For example silver is known to react intensively with iodine compounds. Silver is also relatively inert material and it is thermally stable. Copper is known to react with some radioiodine species. However, it is not reactive toward methyl iodide. In addition, it is oxidized to copper oxide under atmospheric conditions. This may limit the industrial use of copper.(au)

  19. A compressed hydrogen gas storage system with an integrated phase change material

    DEFF Research Database (Denmark)

    Mazzucco, Andrea; Rothuizen, Erasmus Damgaard; Jørgensen, Jens Erik


    change material, mainly occurs after the fueling is completed, resulting in a higher hydrogen peak temperature inside the tank and a lower fuelled mass than a gas-cooled system. Such a mass reduction accounts for 12% with respect to the case of a standard tank system fuelled at -40 °C.......A dynamic fueling model is built to simulate the fueling process of a hydrogen tank with an integrated passive cooling system. The study investigates the possibility of absorbing a part of the heat of compression in the high latent-heat material during melting, with the aim of keeping the walls...... below the critical temperature of 85 °C, while filling the hydrogen at ambient temperature. Results show that a 10-mm-thick layer of paraffin wax can absorb enough heat to reduce the adiabatic temperature by 20 K when compared to a standard Type IV tank. The heat transfer from the gas to the phase...

  20. Thermal decomposition of silane to form hydrogenated amorphous Si (United States)

    Strongin, M.; Ghosh, A.K.; Wiesmann, H.J.; Rock, E.B.; Lutz, H.A. III

    Hydrogenated amorphous silicon is produced by thermally decomposing silane (SiH/sub 4/) or other gases comprising H and Si, at elevated temperatures of about 1700 to 2300/sup 0/C, in a vacuum of about 10/sup -8/ to 10/sup -4/ torr. A gaseous mixture is formed of atomic hydrogen and atomic silicon. The gaseous mixture is deposited onto a substrate to form hydrogenated amorphous silicon.

  1. Development of antibacterial quaternary ammonium silane coatings on polyurethane catheters

    Czech Academy of Sciences Publication Activity Database

    Zanini, S.; Polissi, A.; Maccagni, E.A.; Dell'Orto, E.C.; Liberatore, Chiara; Riccardi, C.


    Roč. 451, Aug (2015), 78-84 ISSN 0021-9797 R&D Projects: GA MŠk EE2.3.20.0143 Grant - others:OP VK 6(XE) CZ.1.07/2.3.00/20.0143 Institutional support: RVO:68378271 Keywords : plasma-induced graft-polymerization * acrylic acid * ATR/FTIR * AFM * quaternary ammonium silane * Escherichia coli Subject RIV: BH - Optics, Masers, Lasers Impact factor: 3.782, year: 2015

  2. Oxidation of elemental mercury by chlorine: Gas phase, Surface,and Photo-induced reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Nai-Qiang; Liu, Shou-Heng; Chang, Shih-Ger


    Accurate oxidation rate constants of mercury gas are needed for determining its dispersion and lifetime in the atmosphere. They would also help in developing a technology for the control of mercury emissions from coal-fired power plants. However, it is difficult to establish the accurate rate constants primarily due to the fact that mercury easily adsorbs on solid surface and its reactions can be catalyzed by the surface. We have demonstrated a procedure that allows the determination of gas phase, surface-induced, and photo-induced contributions in the kinetic study of the oxidation of mercury by chlorine gas. The kinetics was studied using reactors with various surface to volume ratios. The effect of the surface and the photo irradiation on the reaction was taken into consideration. The pressure dependent study revealed that the gas phase oxidation was a three-body collision process. The third order rate constant was determined to be 7.5({+-}0.2) x 10{sup -39} mL{sup 2} molecules{sup -2}s{sup -1} with N{sub 2} as the third body at 297 {+-} 1 K. The surface induced reaction on quartz window was second order and the rate constant was 2.7 x 10{sup -17} mL{sup 2} molecules{sup -1} cm{sup -2} sec. Meanwhile, the 253.7 nm photon employed for mercury detection was found to accelerate the reaction. The utilization efficiency of 253.7 nm photon for Hg{sup 0} oxidation was 6.7 x 10{sup -4} molecules photon{sup -1} under the conditions employed in this study.

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

    International Nuclear Information System (INIS)

    Jorge, Nelly Lidia; Romero, Jorge Marcelo; Grand, André; Hernández-Laguna, Alfonso


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)


    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.

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

    DEFF Research Database (Denmark)

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


    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....... The properties of the model are calculated by Monte Carlo computer-simulation techniques. The two temperatures and the external drive on the system lead to a rich phase diagram including regions of microstructured phases in addition to macroscopically ordered (phase-separated) and disordered phases. Depending...

  6. Electroless silver plating on tetraethoxy silane-bridged fiber glass

    International Nuclear Information System (INIS)

    Lien, Wan-Fu; Huang, Po-Chen; Tseng, Shi-Chang; Cheng, Chia-Hsiang; Lai, Shih-Ming; Liaw, Wen-Chang


    Tetraethoxy silane was used to functionalize the surface of fiber glass (FG) for adsorption with the electroless plated silver shell. The performance of electroless silver plated FG with tetraethoxy silane modification was compared to that of unmodified FG in terms of mechanical and electrical properties. The silane bridge provided more stability for binding with different concentrations of electroless plating silver ions. The characterization was investigated by using field emission scanning electron microscope (FESEM), X-ray diffraction patterns (XRD), energy-dispersion X-ray (EDX), metal microscope (MM) and electric resistance. The Ag coating on TEOS modified FG was more durable than that of unmodified FG in the ball milling test, as confirmed by the data of electric resistance and residue weight. The optimized conditions for producing the Ag coating FG were also investigated. The Ag-Si-FG-3-c product in this study has the lowest electrical resistance of 1.56 × 10 3 Ω/cm 2 and good mechanical stability as exhibited in ball milling tests.

  7. Gas-Phase Thermal Tautomerization of Imidazole-Acetic Acid: Theoretical and Computational Investigations

    Directory of Open Access Journals (Sweden)

    Saadullah G. Aziz


    Full Text Available The gas-phase thermal tautomerization reaction between imidazole-4-acetic (I and imidazole-5-acetic (II acids was monitored using the traditional hybrid functional (B3LYP and the long-range corrected functionals (CAM-B3LYP and ωB97XD with 6-311++G** and aug-cc-pvdz basis sets. The roles of the long-range and dispersion corrections on their geometrical parameters, thermodynamic functions, kinetics, dipole moments, Highest Occupied Molecular Orbital–Lowest Unoccupied Molecular Orbital (HOMO–LUMO energy gaps and total hyperpolarizability were investigated. All tested levels of theory predicted the preference of I over II by 0.750–0.877 kcal/mol. The origin of predilection of I is assigned to the H-bonding interaction (nN8→σ*O14–H15. This interaction stabilized I by 15.07 kcal/mol. The gas-phase interconversion between the two tautomers assumed a 1,2-proton shift mechanism, with two transition states (TS, TS1 and TS2, having energy barriers of 47.67–49.92 and 49.55–52.69 kcal/mol, respectively, and an sp3-type intermediate. A water-assisted 1,3-proton shift route brought the barrier height down to less than 20 kcal/mol in gas-phase and less than 12 kcal/mol in solution. The relatively high values of total hyperpolarizability of I compared to II were interpreted and discussed.

  8. Delivering Transmembrane Peptide Complexes to the Gas Phase Using Nanodiscs and Electrospray Ionization (United States)

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


    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.

  9. Evolution of Molecular and Atomic Gas Phases in the Milky Way (United States)

    Koda, Jin; Scoville, Nick; Heyer, Mark


    We analyze radial and azimuthal variations of the phase balance between the molecular and atomic interstellar medium (ISM) in the Milky Way (MW) using archival CO(J = 1-0) and HI 21 cm data. In particular, the azimuthal variations—between the spiral arm and interarm regions—are analyzed without any explicit definition of the spiral arm locations. We show that the molecular gas mass fraction, I.e., {f}{{mol}}={{{Σ }}}{{{H}}2}/({{{Σ }}}{HI}+{{{Σ }}}{{{H}}2}), varies predominantly in the radial direction: starting from ˜ 100% at the center, remaining ≳ 50% to R˜ 6 {{kpc}} and decreasing to ˜10%-20% at R=8.5 {{kpc}} when averaged over the whole disk thickness (from ˜100% to ≳60%, then to ˜50% in the midplane). Azimuthal, arm-interarm variations are secondary: only ˜ 20% in the globally molecule-dominated inner MW, but becoming larger, ˜40%-50%, in the atom-dominated outskirts. This suggests that in the inner MW the gas remains highly molecular ({f}{{mol}}\\gt 50%) as it moves from an interarm region into a spiral arm and back into the next interarm region. Stellar feedback does not dissociate molecules much, and the coagulation and fragmentation of molecular clouds dominate the evolution of the ISM at these radii. The trend differs in the outskirts where the gas phase is globally atomic ({f}{{mol}}\\lt 50%). The HI and H2 phases cycle through spiral arm passage there. These different regimes of ISM evolution are also seen in external galaxies (e.g., the LMC, M33, and M51). We explain the radial gradient of {f}{{mol}} using a simple flow continuity model. The effects of spiral arms on this analysis are illustrated in the Appendix.

  10. Development of gas-phase sample-introduction techniques for analytical atomic spectrometry. (United States)

    Nakahara, Taketoshi


    For the last 30 years, several types of gas-phase sample-introduction methods in analytical atomic spectrometry, i.e., atomic absorption spectrometry (AAS), atomic emission spectrometry (AES) and atomic fluorescence spectrometry (AFS), have been investigated and developed in the author's laboratory. Their fundamental results are summarized in this review article. The gas-phase sample-introduction techniques developed in the author's laboratory can be roughly divided into four groups: i) hydride generation, ii) cold-vapor generation of mercury, iii) analyte volatilization reactions and iv) miscellaneous. The analytical figures of merit of the gas-phase sample-introduction methods have been described in detail. Hydride generation has been coupled with the AAS of As, Bi, Ge, Pb, Sb, Se, Sn and Te, with the inductively coupled plasma (ICP) AES of As, Bi, Sn, Se and Sb, with the high-power nitrogen microwave-induced plasma (N2-MIP) AES of As, Bi, Pb, Sb, Se, Sn and Te by their single- and multi-element determinations, with the AFS of As, Bi, Pb, Sb, Se, Sn and Te, and with the ICP mass spectrometry (MS) of As and Se. The cold-vapor generation method for Hg has been combined with atmospheric-pressure helium microwave-induced plasma (He- or Ar-MIP)-AES and AFS. Furthermore, analyte volatilization reactions have been employed in the ICP-AES of iodine, in the He-MIP-AES of iodine bromine, chlorine, sulfur and carbon, and in the ICP-MS of sulfur. As a result, when compared with conventional solution nebulization, a great improvement in the sensitivity has been attained in each instance. In addition, the developed techniques coupled with analytical atomic spectrometry have been successfully applied to the determination of trace elements in a variety of practical samples.

  11. High performance liquid chromatographic separations of gas oil samples and their hydrotreated products using commercial normal phases. (United States)

    Oro, Nicole E; Lucy, Charles A


    Three commercially available high performance liquid chromatography columns are used in normal phase or quasi-normal phase mode for the separation of gas oil samples. The columns are tested with 20 analytical standards to determine their suitability for separations of petroleum samples and their ability to separate the nitrogen group-types (pyrrole and pyridine) found in petroleum. The columns studied are polymeric hypercrosslinked polystyrene (HGN), a biphenyl phase, and a Chromegabond "DNAP" column from ES Industries. The HGN column separates gas oils based on both ring structure and heteroatom, while the biphenyl phase has low retention of most compounds studied in quasi-normal phase mode. The "DNAP" column is selective for nitrogen-containing compounds, separating them from PAHs as well as oxygen and sulphur compounds. Retention data of standards on all three columns is shown, along with chromatograms of gas oil samples on the HGN and "DNAP" columns. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. Gas Phase Vibrational Spectroscopy of Weakly Volatil Safe Taggants Using a Synchrotron Source (United States)

    Cuisset, Arnaud; Hindle, Francis; Mouret, Gael; Gruet, Sebastien; Pirali, Olivier; Roy, Pascale


    The high performances of the AILES beamline of SOLEIL allow to study at medium resolution (0.5 cm^{-1}) the gas phase THz vibrational spectra of weakly volatil compounds. Between 2008 and 2010 we recorded and analyzed the THz/Far-IR spectra of phosphorous based nerve agents thanks to sufficient vapour pressures from liquid samples at room temperature. Recently, we extended these experiments towards the vibrational spectroscopy of vapour pressures from solid samples. This project is quite challenging since we target lower volatile compounds, and so requires very high sensitive spectrometers. Moreover a specially designed heated multipass-cell have been developped for the gas phase study of very weak vapor pressures. Thanks to skills acquired during initial studies and recent experiments performed on AILES with solid PAHs, we have recorded and assigned the gas phase vibrational fingerprints from the THz to the NIR spectral domain (10-4000 cm-1) of a set of targeted nitro-derivatives. The study was focused onto the para, ortho-mononitrotoluene (p-NT, o-NT), the 1,4 Dinitrobenzene (1,4 DNB), the 2,3-dimethyl-2,3-dinitrobutane (DMNB), and 2,4 and 2,6-dinitrotoluene (2,4-2,6 DNT), which are safe taggants widely used for the detection of commercial explosives. These taggants are usually added to plastic explosives in order to facilitate their vapour detection. Therefore, there is a continuous interest for their detection and identification in realistic conditions via optical methods. A first step consists in the recording of their gas phase vibrational spectra. These expected spectra focused onto molecules involved into defence and security domains are not yet available to date and will be very useful for the scientific community. This work is supported by the contract ANR-11-ASTR-035-01. A. Cuisset, G. Mouret, O. Pirali, P. Roy, F. Cazier, H. Nouali, J. Demaison, J. Phys. Chem. B, 2008, 112:, 12516-12525 I. Smirnova, A. Cuisset, R. Bocquet, F. Hindle, G. Mouret, O

  13. Gas-Phase Photocatalytic Oxidation of Dimethylamine: The Reaction Pathway and Kinetics

    Directory of Open Access Journals (Sweden)

    Anna Kachina


    Full Text Available Gas-phase photocatalytic oxidation (PCO and thermal catalytic oxidation (TCO of dimethylamine (DMA on titanium dioxide was studied in a continuous flow simple tubular reactor. Volatile PCO products of DMA included ammonia, formamide, carbon dioxide, and water. Ammonia was further oxidized in minor amounts to nitrous oxide and nitrogen dioxide. Effective at 573 K, TCO resulted in the formation of ammonia, hydrogen cyanide, carbon monoxide, carbon dioxide, and water. The PCO kinetic data fit well to the monomolecular Langmuir-Hinshelwood model, whereas TCO kinetic behaviour matched the first-order process. No deactivation of the photocatalyst during the multiple long-run experiments was observed.

  14. Enantioselective supramolecular devices in the gas phase. Resorcin[4]arene as a model system

    Directory of Open Access Journals (Sweden)

    Caterina Fraschetti


    Full Text Available This review describes the state-of-art in the field of the gas-phase reactivity of diastereomeric complexes formed between a chiral artificial receptor and a biologically active molecule. The presented experimental approach is a ligand-displacement reaction carried out in a nano ESI-FT-ICR instrument, supported by a thermodynamic MS-study and molecular-mechanics and molecular-dynamics (MM/MD computational techniques. The noncovalent ion–molecule complexes are ideal for the study of chiral recognition in the absence of complicating solvent and counterion effects.

  15. Wettability in the liquid Cu-Ag alloy – fireproof material – gas phase system

    Directory of Open Access Journals (Sweden)

    G. Siwiec


    Full Text Available In the present paper, results of wettability studies on the liquid metal – fireproof material – gas phase system using copper and Cu-Ag alloys as well as typical fireproof materials, i.e. aluminium oxide, magnesium oxide and graphite, are presented. Contact angle measurements were conducted at 1 373–1 573 K by means of a high-temperature microscope coupled with a camera and a computer equipped with a program for recording and analysing images. For the measurements, the sessile drop method was used.

  16. Solvation of ions in the gas-phase: a molecular dynamics simulation (United States)

    Cabarcos, Orlando M.; Lisy, James M.


    Molecular dynamics simulations have been performed on the collision between a cesium ion and a cluster of twenty methanol molecules. This process, generating a solvated ion, was studied over a range (1 to 25 eV) of eight collision energies. Preliminary analysis of this gas phase solvation has included the distribution of final ion cluster sizes, fragmentation patterns, solvation timescales and energetics. Two distinct patterns have emerged: a ballistic penetration of the neutral cluster at the higher collision energies and an evaporative evolution of the cluster ion at lower collision energies.

  17. Formation and emissions of carbonyls during and following gas-phase ozonation of indoor materials

    DEFF Research Database (Denmark)

    Poppendieck, D.G.; Hubbard, H.F.; Weschler, Charles J.


    Ozone concentrations that are several orders of magnitude greater than typical urban ambient concentrations are necessary for gas-phase ozonation of buildings, either for deodorization or for disinfection of biological agents. However, there is currently no published literature on the interaction...... relatively high BOBP releases. The greatest overall BOBP mass releases were observed for three materials that building occupants might have significant contact with: paper, office partition, and medium density fiberboard, e.g., often used in office furniture. These materials also exhibited extended BOBP...

  18. Ab initio studies of aspartic acid conformers in gas phase and in solution. (United States)

    Chen, Mingliang; Lin, Zijing


    Systematic and extensive conformational searches of aspartic acid in gas phase and in solution have been performed. For the gaseous aspartic acid, a total of 1296 trial canonical structures and 216 trial zwitterionic structures were generated by allowing for all combinations of internal single-bond rotamers. All the trial structures were optimized at the B3LYP/6-311G* level and then subjected to further optimization at the B3LYP/6-311++G** level. A total of 139 canonical conformers were found, but no stable zwitterionic structure was found. The rotational constants, dipole moments, zero-point vibrational energies, harmonic frequencies, and vertical ionization energies of the canonical conformers were determined. Single-point energies were also calculated at the MP2/6-311++G** and CCSD/6-311++G** levels. The equilibrium distributions of the gaseous conformers at various temperatures were calculated. The proton affinity and gas phase basicity were calculated and the results are in excellent agreement with the experiments. The conformations in the solution were studied with different solvation models. The 216 trial zwitterionic structures were first optimized at the B3LYP/6-311G* level using the Onsager self-consistent reaction field model (SCRF) and then optimized at the B3LYP/6-311++G** level using the conductorlike polarized continuum model (CPCM) SCRF theory. A total of 22 zwitterions conformers were found. The gaseous canonical conformers were combined with the CPCM model and optimized at the B3LYP/6-311++G** level. The solvated zwitterionic and canonical structures were further examined by the discrete/SCRF model with one and two water molecules. The incremental solvation of the canonical and zwitterionic structures with up to six water molecules in gas phase was systematically examined. The studies show that combining aspartic acid with at least six water molecules in the gas phase or two water molecules and a SCRF solution model is required to provide

  19. Phase matching of high-order harmonics in a semi-infinite gas cell

    International Nuclear Information System (INIS)

    Steingrube, Daniel S.; Vockerodt, Tobias; Schulz, Emilia; Morgner, Uwe; Kovacev, Milutin


    Phase matching of high-order harmonic generation is investigated experimentally for various parameters in a semi-infinite gas-cell (SIGC) geometry. The optimized harmonic yield is identified using two different noble gases (Xe and He) and its parameter dependence is studied in a systematic way. Beside the straightforward setup of the SIGC, this geometry promises a high photon flux due to a large interaction region. Moreover, since the experimental parameters within this cell are known accurately, direct comparison to simulations is performed. Spectral splitting and blueshift of high-order harmonics are observed.

  20. Gas-Phase Anionic ?-Adduct (Trans)formations in Heteroaromatic Systems1


    Zimnicka, Magdalena; Danikiewicz, Witold


    Anions of nitroderivatives of thiophene and furan were subjected to the reactions with selected C-H acids in the gas phase. Various structures and reaction pathways were proposed for the observed ionic products. In general, the reactions of heteroaromatic anions with C-H acids may be divided into three groups, depending on the proton affinity difference between C-H acid?s conjugate base and heteroaromatic anion (?PA). The proton transfer from C-H acid to heteroaromatic anion is a dominant pro...

  1. Predicting dermal absorption of gas-phase chemicals: transient model development, evaluation, and application

    DEFF Research Database (Denmark)

    Gong, M.; Zhang, Y.; Weschler, Charles J.


    A transient model is developed to predict dermal absorption of gas-phase chemicals via direct air-to-skin-to-blood transport under non-steady-state conditions. It differs from published models in that it considers convective mass-transfer resistance in the boundary layer of air adjacent to the skin....... Results calculated with this transient model are in good agreement with the limited experimental results that are available for comparison. The sensitivity of the modeled estimates to key parameters is examined. The model is then used to estimate air-to-skin-to-blood absorption of six phthalate esters...

  2. Gas-phase hydrosilylation of cyclohexene in an experimental radiation-chemical accelerator apparatus

    International Nuclear Information System (INIS)

    Pecherkin, A.S.; Sidorov, V.I.; Chernyshev, E.A.


    A process for the synthesis of methylcyclohexyldichlorosilane (a basic monomer for the production of organosilicon photoresists) has been investigated and perfected on an experimental apparatus with an ELV-2 electron accelerator; this synthesis involves gas-phase radiation-induced hydrosilylation of cyclohexene by methyldichlorosilane. Basic characteristics of the yield of the desired product under static conditions were determined. With the help of experiments on the synthesis of methylcyclohexyldichlorosilane in a flow- through mode, the technical features of the process of radiation-chemical hydrosilylation of cyclohexene on an accelerator apparatus were determined and studied, the optimal conditions for the synthesis were determined, and an experimental batch of the desired product was produced

  3. Resin adhesion strengths to zirconia ceramics after primer treatment with silane coupling monomer or oligomer. (United States)

    Okada, Masahiro; Inoue, Kazusa; Irie, Masao; Taketa, Hiroaki; Torii, Yasuhiro; Matsumoto, Takuya


    Resin bonding to zirconia ceramics is difficult to achieve using the standard methods for conventional silica-based dental ceramics, which employ silane coupling monomers as primers. The hypothesis in this study was that a silane coupling oligomer -a condensed product of silane coupling monomers- would be a more suitable primer for zirconia. To prove this hypothesis, the shear bond strengths between a composite resin and zirconia were compared after applying either a silane coupling monomer or oligomer. The shear bond strength increased after applying a non-activated ethanol solution of the silane coupling oligomer compared with that achieved when applying the monomer. Thermal treatment of the zirconia at 110°C after application of the silane coupling agents was essential to improve the shear bond strength between the composite resin cement and zirconia.

  4. Rebonding performance of different ceramic brackets conditioned with a new silane coupling agent. (United States)

    Falkensammer, Frank; Jonke, Erwin; Bertl, Michael; Freudenthaler, Josef; Bantleon, Hans Peter


    The objective of this study was to investigate the rebonding effect of a new silane coupling agent on various ceramic brackets bonded to ceramic specimen. Different ceramic brackets (Fascination 2, Clarity SL, and In-OvationC) were assigned to three groups: rebonding with new silane coupling agent, rebonding with conventional silane coupling agent, or regular bonding as control (n = 16). Bracket adhesion was calculated with a shear test in a universal testing machine. The bracket-composite-ceramic interface was evaluated using the adhesive remnant index score. One-way analysis of variance was applied for inferential statistics. Rebonding with the new silane coupling agent resulted in high shear bond strengths (SBSs; mean values: 37.44-41.24 MPa) and ceramic specimen fractures. Rebonding with the conventional silane coupling agent resulted in significantly (P silane coupling should be debonded cautiously using alternative debonding methods.

  5. Surface characterization and cytocompatibility evaluation of silanized magnesium alloy AZ91 for biomedical applications

    Directory of Open Access Journals (Sweden)

    Agnieszka Witecka, Akiko Yamamoto, Henryk Dybiec and Wojciech Swieszkowski


    Full Text Available Mg alloys with high Al contents have superior corrosion resistance in aqueous environments, but poor cytocompatibility compared to that of pure Mg. We have silanized the cast AZ91 alloy to improve its cytocompatibility using five different silanes: ethyltriethoxysilane (S1, 3-aminopropyltriethoxysilane (S2, 3-isocyanatopyltriethoxysilane (S3, phenyltriethoxysilane (S4 and octadecyltriethoxysilane (S5. The surface hydrophilicity/hydrophobicity was evaluated by water contact angle measurements. X-ray photoelectron analysis was performed to investigate the changes in surface states and chemical composition. All silane reagents increased adsorption of the albumin to the modified surface. In vitro cytocompatibility evaluation revealed that silanization improved cell growth on AZ91 modified by silane S1. Measurement of the concentration of Mg2+ ions released during the cell culture indicated that silanization does not affect substrate degradation.

  6. Low Cost Solar Array Project. Feasibility of the silane process for producing semiconductor-grade silicon. Final report, October 1975-March 1979

    Energy Technology Data Exchange (ETDEWEB)


    The commercial production of low-cost semiconductor-grade silicon is an essential requirement of the JPL/DOE (Department of Energy) Low-Cost Solar Array (LSA) Project. A 1000-metric-ton-per-year commercial facility using the Union Carbide Silane Process will produce molten silicon for an estimated price of $7.56/kg (1975 dollars, private financing), meeting the DOE goal of less than $10/kg. Conclusions and technology status are reported for both contract phases, which had the following objectives: (1) establish the feasibility of Union Carbide's Silane Process for commercial application, and (2) develop an integrated process design for an Experimental Process System Development Unit (EPSDU) and a commercial facility, and estimate the corresponding commercial plant economic performance. To assemble the facility design, the following work was performed: (a) collection of Union Carbide's applicable background technology; (b) design, assembly, and operation of a small integrated silane-producing Process Development Unit (PDU); (c) analysis, testing, and comparison of two high-temperature methods for converting pure silane to silicon metal; and (d) determination of chemical reaction equilibria and kinetics, and vapor-liquid equilibria for chlorosilanes.

  7. Gas-liquid two-phase flow behavior in terrain-inclined pipelines for gathering transport system of wet natural gas

    DEFF Research Database (Denmark)

    Yang, Yan; Li, Jingbo; Wang, Shuli


    The Volume of Fluid method and Re-Normalisation Group (RNG) k-ε turbulence model were employed to predict the gas-liquid two-phase flow in a terrain-inclined pipeline with deposited liquids. The simulation was carried out in a 22.5 m terrain-inclined pipeline with a 150 mm internal diameter...... on the liquid level under the suction force which caused by the negative pressure around the elbow, and then it touched to the top of the pipe. When the liquid blocked the pipe, the pressure drop between the upstream and downstream of the elbow increased with the increase of the gas velocity. At larger gas...

  8. Catalytic Gas-Phase Production of Lactide from Renewable Alkyl Lactates. (United States)

    De Clercq, Rik; Dusselier, Michiel; Makshina, Ekaterina; Sels, Bert F


    A new route to lactide, which is a key building block of the bioplastic polylactic acid, is proposed involving a continuous catalytic gas-phase transesterification of renewable alkyl lactates in a scalable fixed-bed setup. Supported TiO 2 /SiO 2 catalysts are highly selective to lactide, with only minimal lactide racemization. The solvent-free process allows for easy product separation and recycling of unconverted alkyl lactates and recyclable lactyl intermediates. The catalytic activity of TiO 2 /SiO 2 catalysts was strongly correlated to their optical properties by DR UV/Vis spectroscopy. Catalysts with high band-gap energy of the supported TiO 2 phase, indicative of a high surface spreading of isolated Ti centers, show the highest turnover frequency per Ti site. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Formation of secondary aerosols over Europe: comparison of two gas-phase chemical mechanisms (United States)

    Kim, Y.; Sartelet, K.; Seigneur, C.


    The impact of two recent gas-phase chemical kinetic mechanisms (CB05 and RACM2) on the formation of secondary inorganic and organic aerosols is compared for simulations of PM2.5 over Europe between 15 July and 15 August 2001. The host chemistry transport model is Polair3D of the Polyphemus air-quality platform. Particulate matter is modeled with a sectional aerosol model (SIREAM), which is coupled to the thermodynamic model ISORROPIA for inorganic species and to a module (MAEC) that treats both hydrophobic and hydrophilic species for secondary organic aerosol (SOA). Modifications are made to the gas-phase chemical mechanisms to handle the formation of SOA. In order to isolate the effect of the original chemical mechanisms on PM formation, the addition of reactions and chemical species needed for SOA formation was harmonized to the extent possible between the two gas-phase chemical mechanisms. Model performance is satisfactory with both mechanisms for speciated PM2.5. The monthly-mean difference of the concentration of PM2.5 is less than 1 μg m-3 (6%) over the entire domain. Secondary chemical components of PM2.5 include sulfate, nitrate, ammonium and organic aerosols, and the chemical composition of PM2.5 is not significantly different between the two mechanisms. Monthly-mean concentrations of inorganic aerosol are higher with RACM2 than with CB05 (+16% for sulfate, +11% for nitrate, and +10% for ammonium), whereas the concentrations of organic aerosols are slightly higher with CB05 than with RACM2 (+22% for anthropogenic SOA and +1% for biogenic SOA). Differences in the inorganic and organic aerosols result primarily from differences in oxidant concentrations (OH, O3 and NO3). Nitrate formation tends to be HNO3-limited over land and differences in the concentrations of nitrate are due to differences in concentration of HNO3. Differences in aerosols formed from aromatic SVOC are due to different aromatic oxidation between CB05 and RACM2. The aromatic oxidation in

  10. A local leaky-box model for the local stellar surface density-gas surface density-gas phase metallicity relation (United States)

    Zhu, Guangtun Ben; Barrera-Ballesteros, Jorge K.; Heckman, Timothy M.; Zakamska, Nadia L.; Sánchez, Sebastian F.; Yan, Renbin; Brinkmann, Jonathan


    We revisit the relation between the stellar surface density, the gas surface density and the gas-phase metallicity of typical disc galaxies in the local Universe with the SDSS-IV/MaNGA survey, using the star formation rate surface density as an indicator for the gas surface density. We show that these three local parameters form a tight relationship, confirming previous works (e.g. by the PINGS and CALIFA surveys), but with a larger sample. We present a new local leaky-box model, assuming star-formation history and chemical evolution is localized except for outflowing materials. We derive closed-form solutions for the evolution of stellar surface density, gas surface density and gas-phase metallicity, and show that these parameters form a tight relation independent of initial gas density and time. We show that, with canonical values of model parameters, this predicted relation match the observed one well. In addition, we briefly describe a pathway to improving the current semi-analytic models of galaxy formation by incorporating the local leaky-box model in the cosmological context, which can potentially explain simultaneously multiple properties of Milky Way-type disc galaxies, such as the size growth and the global stellar mass-gas metallicity relation.

  11. Numerical Simulations of Liquid-Gas-Solid Three-Phase Flows in Microgravity

    Directory of Open Access Journals (Sweden)

    Xinyu Zhang


    Full Text Available Three-phase liquid-gas-solid flows under microgravity condition are studied. An Eulerian-Lagrangian computational model was developed and used in the simulations. In this approach, the liquid flow was modeled by a volume-averaged system of governing equations, whereas motions of particles and bubbles were evaluated using the Lagrangian trajectory analysis procedure. It was assumed that the bubbles remained spherical, and their shape variations were neglected. The bubble-liquid, particle-liquid and bubbl-particle two-way interactions were accounted for in the analysis. The discrete phase equations used included drag, lift, buoyancy, and virtual mass forces. Particle-particle interactions and bubble-bubble interactions were accounted for by the hard sphere model. Bubble coalescence was also included in the model. The transient flow characteristics of the three-phase flow were studied; and the effects of gravity, inlet bubble size and g-jitter acceleration on variation of flow characteristics were discussed. The low gravity simulations showed that most bubbles are aggregated in the inlet region. Also, under microgravity condition, bubble transient time is much longer than that in normal gravity. As a result, the Sauter mean bubble diameter, which is proportional to the transient time of the bubble, becomes rather large, reaching to more than 9 mm. The bubble plume in microgravity exhibits a plug type flow behavior. After the bubble plume reaches the free surface, particle volume fraction increases along the height of the column. The particles are mainly located outside the bubble plume, with very few particles being retained in the plume. In contrast to the normal gravity condition, the three phases in the column are poorly mixed under microgravity conditions. The velocities of the three phases were also found to be of the same order. Bubble size significantly affects the characteristics of the three-phase flows under microgravity conditions. For

  12. The health significance of gas- and particle-phase terpene oxidation products: a review. (United States)

    Rohr, Annette C


    The reactions between terpenes and ozone (or other oxidants) produce a wide variety of both gas- and particle-phase products. Terpenes are biogenic volatile organic compounds (VOCs) that are also contained in many consumer products. Ozone is present indoors since it infiltrates into the indoor environment and is emitted by some office and consumer equipment. Some of the gaseous products formed are irritating to biological tissues, while the condensed-phase products have received attention due to their contribution to ambient fine particulate matter (PM2.5) and its respective health significance. Despite common scientific questions, the indoor and ambient air research communities have tended to operate in isolation regarding this topic. This review critically evaluates the literature related to terpene oxidation products and attempts to synthesize results of indoor and ambient air studies to better understand the health significance of these materials and identify knowledge gaps. The review documents the results of a literature search covering terpene oxidation chemistry, epidemiological, toxicological, and controlled human exposure studies, as well as health studies focused more generically on secondary organic aerosol (SOA). The literature shows a clear role for gas-phase terpene oxidation products in adverse airway effects at high concentrations; however, whether these effects occur at more environmentally relevant levels is unclear. The evidence for toxicity of particle-phase products is less conclusive. Knowledge gaps and future research needs are outlined, and include the need for more consistency in study designs, incorporation of reaction product measurements into epidemiological studies conducted in both indoor and ambient settings, and more focused research on the toxicity of SOA, especially SOA of biogenic origin. © 2013.

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

    Energy Technology Data Exchange (ETDEWEB)

    Marcos Dantus


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

  14. Mixing in three-phase systems: Implications for enhanced oil recovery and unconventional gas extraction (United States)

    Jimenez-Martinez, J.; Porter, M. L.; Hyman, J.; Carey, J. W.; Viswanathan, H. S.


    Although the mixing of fluids within a porous media is a common process in natural and industrial systems, how the degree of mixing depends on the miscibility of multiple phases is poorly characterized. Often, the direct consequence of miscible mixing is the modification of the resident fluid (brine and hydrocarbons) rheological properties. We investigate supercritical (sc)CO2 displacement and mixing processes in a three-phase system (scCO2, oil, and H2O) using a microfluidics experimental system that accommodates the high pressures and temperatures encountered in fossil fuel extraction operations. The miscibility of scCO2 with the resident fluids, low with aqueous solutions and high with hydrocarbons, impacts the mixing processes that control sweep efficiency in enhanced oil recovery (EOR) and the unlocking of the system in unconventional oil and gas extraction. Using standard volume-averaging techniques we upscale the aqueous phase saturation to the field-scale (i.e., Darcy scale) and interpret the results as a simpler two-phase system. This process allows us to perform a statistical analysis to quantify i) the degree of heterogeneity in the system resulting from the immiscible H2O and ii) how that heterogeneity impacts mixing between scCO2 and oil and their displacement. Our results show that when scCO2 is used for miscible displacement, the presence of an aqueous solution, which is common in secondary and tertiary EOR and unconventional oil and gas extraction, strongly impacts the mixing of scCO2 with the hydrocarbons due to low scCO2-H2O miscibility. H2O, which must be displaced advectively by the injected scCO2, introduces spatio-temporal variability into the system that acts as a barrier between the two miscibile fluids. This coupled with the effect of viscosity contrast, i.e., viscous fingering, has an impact on the mixing of the more miscible pair.

  15. Effects of silane-modified fillers on properties of dental composite resin. (United States)

    Aydınoğlu, Aysu; Yoruç, Afife Binnaz Hazar


    The effect of silanization on the mechanical, chemical, and physical properties of dental composites was investigated. Silica fillers were obtained from colloidal silica solution, Ludox® HS-40 and they were silanized by using 3-methacryloxypropyl trimethoxysilane (MPTMS) in an acidic media. Mineralogical and chemical structures of unsilanized and silanized fillers were determined by using XRD and FT-IR analyses. The modification of unsilanized/silanized fillers were investigated by performing XPS and TGA analyses. The morphological evaluations, surface area, and particle size measurements were performed by using SEM, BET, and Zeta-Sizer, respectively. Eventually, pure and amorphous silica fillers were obtained. Furthermore, the weight percentage of the silane in silica/silane structure was compatible with theoretical values. SEM images, surface area, and particle size measurements showed that agglomeration tendencies of silanized fillers were lower compared to silanized fillers because of the MPTMS addition. Experimental composites (5/10/10/5BisGMA/HEMA/UDMA/TEGDMA resin reinforced with 70wt% silanized/unsilanized SiO 2 ) were fabricated into 4mm diameter×6mm thick discs for compressive strength (CS), angular flexural strength (AFS), curing depth (CD), and polymerization shrinkage (PS) on a 25×2×2mm rectangular Teflon mold for flexural strength (FS) and modulus of elasticity (E) tests. The curing depth (CD) and degree of polymerization percentage (DP) of composites were determined. Consequently, results showed that mechanical properties and DP of composite resins can be greatly influenced by silanization as a result of the organic matrix-inorganic filler interface bonding formed by silane structures. Despite of these findings, silanization of the SiO 2 was not effected DC and PS values. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Flow-pattern identification and nonlinear dynamics of gas-liquid two-phase flow in complex networks. (United States)

    Gao, Zhongke; Jin, Ningde


    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.

  17. Pigging analysis for gas-liquid two phase flow in pipelines

    International Nuclear Information System (INIS)

    Kohda, K.; Suzukawa, Y.; Furukawa, H.


    A new method to analyze transient phenomena caused by pigging in gas-liquid two-phase flow is developed. During pigging, a pipeline is divided into three sections by two moving boundaries, namely the pig and the leading edge of the liquid slug in front of the pig. The basic equations are mass, momentum and energy conservation equations. The boundary conditions at the moving boundaries are determined from the mass conservation across the boundaries, etc. A finite difference method is used to solve the equations numerically. The method described above is also capable of analyzing transient two-phase flow caused by pressure and flow rate changes. Thus the over-all analysis of transient two-phase flow in pipelines becomes possible. A series of air-water two-phase flow pigging experiments was conducted using 105.3 mm diameter and 1436.5 m long test pipeline. The agreement between the measured and the calculated results is very good

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

    CERN Document Server

    Gao, Zhong-Ke; Wang, Wen-Xu


    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 ...

  19. Graphite-supported platinum catalysts: Effects of gas and aqueous phase treatments

    Energy Technology Data Exchange (ETDEWEB)

    Vleeming, J.H.; Kuster, B.F.M.; Marin, G.B. [Eindhoven Univ. of Technology (Netherlands)] [and others


    The effects on the platinum particle diameter and the available platinum surface area of a graphite-supported platinum catalyst resulting from pretreatments and from performing a selective oxidation reaction are investigated. In the gas phase considerable catalyst sintering occurs only in the presence of oxygen at 773 K due to extensive carbon burn-off, whereas in an aqueous phase platinum particle growth is limited upon oxidative treatment. A hydrogen treatment in aqueous phase at 363 K causes platinum particle growth, aggregate formation, and covering of metal sites. These phenomena become more important with increasing pH. Platinum particle growth and aggregate formation are attributed to platinum particle rather than platinum adatom mobility and is caused by the destruction of the oxygen-containing surface groups on the graphite support, which serve as anchorage sites for the platinum particles. Site covering is caused by products originating from the graphite support, which are formed as a result of the reductive treatments. When performing the aqueous phase oxidation of methyl {alpha}-D-glucopyranoside at 323 K and a pH of 9, catalyst modifications are small under oxidative conditions. Exposure of the catalyst for several hours to methyl {alpha}-D-glucopyranoside under the same conditions but in the absence of oxygen causes site covering. 50 refs., 9 figs., 1 tab.

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

    DEFF Research Database (Denmark)

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


    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...... conditions. Lysozyme ions bound by an oligosaccharide incorporated less deuterium than the unbound ion. Similarly, trypsin ions showed reduced deuterium uptake when bound by the peptide ligand vasopressin. Our results are in good agreement with crystal structures of the native protein complexes......, and illustrate that gas-phase HDX-MS can provide a sensitive and simple approach to measure the number of heteroatom-bound non-amide side-chain hydrogens involved in the binding interface of biologically relevant protein complexes....

  1. Surface modification of basalt with silane coupling agent on asphalt mixture moisture damage

    Energy Technology Data Exchange (ETDEWEB)

    Min, Yahong; Fang, Ying; Huang, Xiaojun; Zhu, Yinhui; Li, Wensheng [College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082 (China); Yuan, Jianmin [College of Materials Engineering, Hunan University, Changsha, 410082 (China); Tan, Ligang [College of Mechanical and Vehicle Engineering, Hunan University, Changsha, 410082 (China); Wang, Shuangyin [State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082 (China); Wu, Zhenjun, E-mail: [College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082 (China)


    Graphical abstract: - Highlights: • A new silane coupling agent was synthesized based on KH570. • Basalt surface was modified using the new silane coupling agent. • Chemical bond between basalt and the new silane coupling agent was formed. • Asphalt mixture which used modified basalt show superior water stability. - Abstract: A new silane coupling agent was synthesized based on γ-(methacryloyloxy) propyltrimethoxysilane (KH570). The surface of basalt rocks was modified by KH570 and the new silane coupling agent (NSCA), and the interfacial interaction between silane coupling agent and basalt was also studied. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis showed that the silane coupling agent molecule bound strongly with basalt rocks. Scanning electronic microscopy (SEM) observation showed that a thin layer of coupling agent was formed on the surface of modified basalt. The boiling test and immersion Marshall test confirmed that the moisture sensitivity of basalt modified with the new silane coupling agent increased more significantly than that untreated and treated with KH570. The Retained Marshall Strength of basalt modified with the new coupling agent increased from 71.74% to 87.79% compared with untreated basalt. The results indicated that the new silane coupling agent played an important role in improving the interfacial performance between basalt and asphalt.

  2. Continuous-wave terahertz by photomixing: applications to gas phase pollutant detection and quantification (United States)

    Hindle, Francis; Cuisset, Arnaud; Bocquet, Robin; Mouret, Gaël


    Recent advances in the development of monochromatic continuous-wave terahertz sources suitable for high resolution gas phase spectroscopy and pollution monitoring are reviewed. Details of a source using an ultra fast opto-electronic photomixing element are presented. The construction of a terahertz spectrometer using this source has allowed spectroscopic characterisation and application studies to be completed. Analysis of H 2S and OCS under laboratory conditions are used to demonstrate the spectrometer performance, and the determination of the transition line strengths and pressure self broadening coefficients for pure rotational transitions of OCS. The spectral purity 5 MHz, tunability 0.3 to 3 THz, and long wavelength ≈200 μm of this source have been exploited to identify and quantify numerous chemical species in cigarette smoke. The key advantages of this frequency domain are its high species selectivity and the possibility to make reliable measurements of gas phase samples heavily contaminated by aerosols and particles. To cite this article: F. Hindle et al., C. R. Physique 9 (2008).

  3. Pulse radiolysis studies of some atomic and molecular processes in the gas phase

    International Nuclear Information System (INIS)

    Hatano, Y.; Takao, S.; Shimamori, H.; Ueno, T.; Yokoyama, A.


    The technique of pulse radiolysis has been applied to the study of some atomic and molecular processes in gas phase. The first application was to the determination of the Penning ionization rate constant. He-N 2 mixture was irradiated with nano-second pulses of 600 keV electrons, and the optical emission of N 2 + was measured. The result was compared with those obtained by other techniques. The second application was to the study of the lowest triplet state of benzene. The triplet state relaxation of benzene in gas phase was studied by measuring the phosphorescence of biacetyl induced by the energy transfer to biacetyl from triplet benzene in the pulse radiolysis of benzene-biacetyl mixture. The third application was to the study of thermal electron attachment to O 2 , in which microwave cavity method combined with pulse radiolysis has been used to observe the disappearance of thermal electrons directly with the fast response by attachment to O 2 . (Aoki, K.)

  4. Synchrotron and small bio-molecules in gas phase and liquid environment: new opportunities in Brazil

    International Nuclear Information System (INIS)

    Naves de Brito, A.


    Full text: Two techniques are critically related to the photoelectric law, namely: photoelectron spectroscopy and photoelectron-photoion coincidence spectroscopy. Both are strongly used now a day within synchrotron laboratories. Our group is employing both to investigate fragmentation of bio-molecules in gas phase such as amino acids and DNA basis using V UV and soft x-ray photons. In the near future lager scale instruments developed in Brazil will allow unique opportunities to apply these two spectroscopic methods to molecules immersed in liquids such as water. We will present details from this advanced x-ray source and experimental stations with capabilities not present in other places in the world. Experiments connected to the molecular origin of live will be shown. Among them an experiment where we mimic the atmosphere at Titan moon producing bio- molecules will discussed. Another experiment will be presented where we test the Panspermia viability using special bacteria. We will also present experiments where frozen simple molecules connected to pre-biotic mate- rial are bombardment by UV photons and energetic particles showing interesting trends. Spectroscopic studies of gas phase photo-fragmentation of bio-molecules may be critical to understand in the future these molecules immersed in liquids. We plan to spend some time showing our recent results in this area. (author)

  5. Gas-Liquid Two-Phase Flows Through Packed Bed Reactors in Microgravity (United States)

    Motil, Brian J.; Balakotaiah, Vemuri


    The simultaneous flow of gas and liquid through a fixed bed of particles occurs in many unit operations of interest to the designers of space-based as well as terrestrial equipment. Examples include separation columns, gas-liquid reactors, humidification, drying, extraction, and leaching. These operations are critical to a wide variety of industries such as petroleum, pharmaceutical, mining, biological, and chemical. NASA recognizes that similar operations will need to be performed in space and on planetary bodies such as Mars if we are to achieve our goals of human exploration and the development of space. The goal of this research is to understand how to apply our current understanding of two-phase fluid flow through fixed-bed reactors to zero- or partial-gravity environments. Previous experiments by NASA have shown that reactors designed to work on Earth do not necessarily function in a similar manner in space. Two experiments, the Water Processor Assembly and the Volatile Removal Assembly have encountered difficulties in predicting and controlling the distribution of the phases (a crucial element in the operation of this type of reactor) as well as the overall pressure drop.

  6. Oxysterols in cosmetics-Determination by planar solid phase extraction and gas chromatography-mass spectrometry. (United States)

    Schrack, S; Hohl, C; Schwack, W


    Sterol oxidation products (SOPs) are linked to several toxicological effects. Therefore, investigation of potential dietary uptake sources particularly food of animal origin has been a key issue for these compounds. For the simultaneous determination of oxysterols from cholesterol, phytosterols, dihydrolanosterol and lanosterol in complex cosmetic matrices, planar solid phase extraction (pSPE) was applied as clean-up tool. SOPs were first separated from more non-polar and polar matrix constituents by normal phase thin-layer chromatography and then focussed into one target zone. Zone extraction was performed with the TLC-MS interface, followed by gas chromatography-mass spectrometry analysis. pSPE showed to be effective for cleaning up cosmetic samples as sample extracts were free of interferences, and gas chromatographic columns did not show any signs of overloading. Recoveries were between 86 and 113% with relative standard deviations of below 10% (n=6). Results of our market survey in 2016 showed that some cosmetics with ingredients of plant origin contained phytosterol oxidation products (POPs) in the low ppm range and therefore in line with levels reported for food. In lanolin containing products, total SOPs levels (cholesterol oxidation products (COPs), lanosterol oxidation products (LOPs), dihydrolanosterol oxidation products (DOPs)) being in the low percent range exceeded reported levels for food by several orders of magnitudes. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    CERN Document Server

    Rondo, L.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.


    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosolnucleation. Based on quantum chemical calculations it has been suggested that the quantitative detectionof gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased inthe presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was setup at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection ofH2SO4in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time inthe CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF(Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutralsulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presenceof dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS...

  8. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry (United States)

    Rondo, L.; Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.


    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

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

    Energy Technology Data Exchange (ETDEWEB)

    Vernieres, Jerome, E-mail:; 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: [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)


    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.

  10. Properties of clusters in the gas phase: V. Complexes of neutral molecules onto negative ions

    International Nuclear Information System (INIS)

    Keesee, R.G.; Lee, N.; Castleman, A.W. Jr.


    Ion--molecules association reactions of the form A - (B)/sub n1/-+B=A - (B)/sub n/ were studied over a range of temperatures in the gas phase using high pressure mass spectrometry. Enthalpy and entropy changes were determined for the stepwise clustering reactions of (1) sulfur dioxide onto Cl - , I - , and NO 2 - with n ranging from one to three or four, and onto SO 2 - and SO 3 - with n equal to one; and (2) carbon dioxide onto Cl - , I - , NO 2 - , CO 3 - , and SO 3 - with n equal to one. From these data and earlier hydration results, the order of the magnitude of the enthalpy changes on the association of the first neutral for a series of negative ions was found to parallel the gas-phase basicity of those anions. For any given ion, the relative order of the addition enthalpies among the neutrals was found to be dependent on the polarizabilities of the neutrals and on the covalency in the ion-neutral bond. Dispersion of charge via covalent bonding was found to affect significantly the succeeding clustering steps

  11. Mapping the conformational free energy of aspartic acid in the gas phase and in aqueous solution. (United States)

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


    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.

  12. Non-stationary filtration mode during chemical reactions with the gas phase (United States)

    Zavialov, Ivan; Konyukhov, Andrey; Negodyaev, Sergey


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

  13. Photochemical reactions of triplet benzophenone and anthraquinone molecules with amines in the gas phase

    International Nuclear Information System (INIS)

    Zalesskaya, G.A.; Sambor, E.G.; Belyi, N.N.


    The intermolecular photoinduced reactions between triplet ketone molecules and aliphatic amines and pyridine are studied by the quenching of delayed fluorescence of anthraquinone and benzophenone vapors by diethylamine, dibutylamine, cyclohexylamine, triethylamine, and pyridine. In the temperature range 423-573 K, the delayed fluorescence quenching rate constants k q are estimated from changes in the decay rate constant and the intensity of delayed fluorescence upon increasing pressure of bath gases. It is ascertained that, in the gas phase, the mixtures under study exhibit both a negative and a positive dependence of k q on temperature, which indicates that some photoinduced reactions do not have activation barriers. The rate constant k q is shown to increase with decreasing ionization potential of the electron donors. This points to the importance of interactions with charge transfer in the photoreaction of triplet ketone molecules with aliphatic amines and pyridine in the gas phase. The relationship between k q and the change in the free energy ΔG upon the photoinduced intermolecular electron transfer, which is the primary stage of the photochemical reaction, is studied. It is shown that the dependence k q (ΔG) for the donor-acceptor pairs under study is described well by the Marcus equation, in which the average vibrational energies of the donor and acceptor are taken into account for the estimate of ΔG

  14. Gas-phase ion-molecule reactions and high-pressure mass spectrometer, 1

    International Nuclear Information System (INIS)

    Hiraoka, Kenzo


    The reasons for the fact that the research in gas-phase ion-molecule reactions, to which wide interest is shown, have greatly contributed to the physical and chemical fields are that, first it is essential in understanding general phenomena concerning ions, second, it can furnish many unique informations in the dynamics of chemical reactions, and third, usefulness of '' chemical ionization'' methods has been established as its application to chemical analysis. In this review, the history and trend of studies and equipments in gas-phase ion-molecule reactions are surveyed. The survey includes the chemical ionization mass spectrometer for simultaneously measuring the positive and negative ions utilizing a quadrupole mass spectrometer presented by Hunt and others, flowing afterglow method derived from the flowing method which traces neutral chemical species mainly optically, ion cyclotron resonance mass spectrometer, trapped ion mass spectrometer and others. Number of reports referred to ion-molecule reactions issued during the last one year well exceeds the total number of reports concerning mass spectrometers presented before 1955. This truly shows how active the research and development are in this field. (Wakatsuki, Y.)

  15. Primary and secondary organic aerosol origin by combined gas-particle phase source apportionment

    Directory of Open Access Journals (Sweden)

    M. Crippa


    Full Text Available Secondary organic aerosol (SOA, a prominent fraction of particulate organic mass (OA, remains poorly constrained. Its formation involves several unknown precursors, formation and evolution pathways and multiple natural and anthropogenic sources. Here a combined gas-particle phase source apportionment is applied to wintertime and summertime data collected in the megacity of Paris in order to investigate SOA origin during both seasons. This was possible by combining the information provided by an aerosol mass spectrometer (AMS and a proton transfer reaction mass spectrometer (PTR-MS. A better constrained apportionment of primary OA (POA sources is also achieved using this methodology, making use of gas-phase tracers. These tracers made possible the discrimination between biogenic and continental/anthropogenic sources of SOA. We found that continental SOA was dominant during both seasons (24–50% of total OA, while contributions from photochemistry-driven SOA (9% of total OA and marine emissions (13% of total OA were also observed during summertime. A semi-volatile nighttime component was also identified (up to 18% of total OA during wintertime. This approach was successfully applied here and implemented in a new source apportionment toolkit.

  16. Fluorescence probe of polypeptide conformational dynamics in gas phase and in solution (United States)

    Iavarone, Anthony T.; Meinen, Jan; Schulze, Susanne; Parks, Joel H.


    Fluorescence measurements of polypeptides derivatized with the fluorescent dye BODIPY TMR have been used to probe the polypeptide conformational dynamics as a function of temperature and charge state. Measurements of (BODIPY TMR)-[Pro]n-Arg-Trp and (BODIPY TMR)-[Gly-Ser]m-Arg-Trp have been performed for charge states 1+ and 2+ of n = 4 and 10 and m = 2 and 5. The 2+ charge states of both of these polypeptides exhibit similar temperature dependences for equal chain lengths (n = 4, m = 2 and n = 10, m = 5) and suggest conformations dominated by Coulomb repulsion. In the absence of such Coulomb repulsion, the 1+ charge state conformations appear to be characterized by the flexibility of the polypeptide chain for which [Gly-Ser]m > [Pro]n. Comparisons of these gas phase polypeptide measurements with corresponding measurements in solution provide a direct measure of the effects of solvent on the conformational dynamics. The change in fluorescence as a function of temperature in the gas phase is two orders of magnitude greater than that in solution, a dramatic result we attribute to the restrictions on intramolecular dynamics imposed by diffusion-limited kinetics and the lack of shielding by solvent. Measurements were also made of unsolvated Pron peptides without the tryptophan (Trp) residue to isolate the interaction of the fluorescent dye with charges.

  17. Sources and potential health risk of gas phase PAHs in Hexi Corridor, Northwest China. (United States)

    Mao, Xiaoxuan; Yu, Zhousuo; Ding, Zhongyuan; Huang, Tao; Ma, Jianmin; Zhang, Gan; Li, Jun; Gao, Hong


    Gas phase polycyclic aromatic hydrocarbons (PAHs) in Hexi Corridor, Northwest China were determined during heating and non-heating seasons, respectively, using passive air samplers. Polyurethane foam (PUF) disks were chosen as the sampling medium. Fifteen PAHs out of the 16 PAHs classified by the United States Environmental Protection Agency (U.S. EPA) were detected in this field sampling investigation. The atmospheric levels of sampled PAHs were higher at urban sites than that at rural sites among 14 sampling sites and increased during heating season. The highest concentration (11.34 ng m(-3)) was observed in Lanzhou during the heating season, the capital and largest industrial city of Gansu Province. PAH contamination in air was dominated by three aromatic ring congeners. Possible sources of PAHs were apportioned using PAH species ratios and the principle component analysis (PCA) combined with a multiple linear regression (MLR) method. Fossil fuel consumption was identified to be the predominant source of PAHs over Hexi Corridor, accounting for 43 % of the concentration of total (15) PAHs. Backward and forward trajectory and cluster analysis were also carried out to identify potential origins of PAHs monitored at several urban and rural sites. Lung cancer risk of local residents to gas phase PAHs via inhalation exposure throughout the province was found to be around a critical value of the lung cancer risk level at 10(-6) recommended by the U.S. EPA risk assessment guideline.

  18. Gas-phase pesticide measurement using iodide ionization time-of-flight mass spectrometry (United States)

    Murschell, Trey; Fulgham, S. Ryan; Farmer, Delphine K.


    Volatilization and subsequent processing in the atmosphere are an important environmental pathway for the transport and chemical fate of pesticides. However, these processes remain a particularly poorly understood component of pesticide lifecycles due to analytical challenges in measuring pesticides in the atmosphere. Most pesticide measurements require long (hours to days) sampling times coupled with offline analysis, inhibiting observation of meteorologically driven events or investigation of rapid oxidation chemistry. Here, we present chemical ionization time-of-flight mass spectrometry with iodide reagent ions as a fast and sensitive measurement of four current-use pesticides. These semi-volatile pesticides were calibrated with injections of solutions onto a filter and subsequently volatilized to generate gas-phase analytes. Trifluralin and atrazine are detected as iodide-molecule adducts, while permethrin and metolachlor are detected as adducts between iodide and fragments of the parent analyte molecule. Limits of detection (1 s) are 0.37, 0.67, 0.56, and 1.1 µg m-3 for gas-phase trifluralin, metolachlor, atrazine, and permethrin, respectively. The sensitivities of trifluralin and metolachlor depend on relative humidity, changing as much as 70 and 59, respectively, as relative humidity of the sample air varies from 0 to 80 %. This measurement approach is thus appropriate for laboratory experiments and potentially near-source field measurements.

  19. Gas-phase pesticide measurement using iodide ionization time-of-flight mass spectrometry

    Directory of Open Access Journals (Sweden)

    T. Murschell


    Full Text Available Volatilization and subsequent processing in the atmosphere are an important environmental pathway for the transport and chemical fate of pesticides. However, these processes remain a particularly poorly understood component of pesticide lifecycles due to analytical challenges in measuring pesticides in the atmosphere. Most pesticide measurements require long (hours to days sampling times coupled with offline analysis, inhibiting observation of meteorologically driven events or investigation of rapid oxidation chemistry. Here, we present chemical ionization time-of-flight mass spectrometry with iodide reagent ions as a fast and sensitive measurement of four current-use pesticides. These semi-volatile pesticides were calibrated with injections of solutions onto a filter and subsequently volatilized to generate gas-phase analytes. Trifluralin and atrazine are detected as iodide–molecule adducts, while permethrin and metolachlor are detected as adducts between iodide and fragments of the parent analyte molecule. Limits of detection (1 s are 0.37, 0.67, 0.56, and 1.1 µg m−3 for gas-phase trifluralin, metolachlor, atrazine, and permethrin, respectively. The sensitivities of trifluralin and metolachlor depend on relative humidity, changing as much as 70 and 59, respectively, as relative humidity of the sample air varies from 0 to 80 %. This measurement approach is thus appropriate for laboratory experiments and potentially near-source field measurements.

  20. Aluminum-doped ZnO nanoparticles: gas-phase synthesis and dopant location (United States)

    Schilling, Carolin; Zähres, Manfred; Mayer, Christian; Winterer, Markus


    Aluminum-doped ZnO (AZO) nanoparticles are studied widely as transparent conducting alternatives for indium tin oxide. However, the properties of AZO vary in different investigations not only with the amount of dopant and the particle size, but also with other parameters such as synthesis method and conditions. Hence, AZO nanoparticles, synthesized in the gas phase, were investigated to study the influence of the synthesis parameters dopant level, reactor temperature and residence time in the reaction zone on the particle characteristics. The local structure of the dopant in semiconductors determines whether the doping is functional, i.e., whether mobile charge carriers are generated. Therefore, information obtained from 27Al solid-state NMR spectroscopy, X-ray diffraction, photoluminescence and UV-Vis spectroscopy was used to understand how the local structure influences particles characteristics and how the local structure itself can be influenced by the synthesis parameters. In addition to AZO particles of different Al content, pure ZnO, Al2O3, ZnAl2O4 and core-shell particles of ZnO and Al2O3 were synthesized for comparison and aid to a deeper understanding of the formation of AZO nanoparticles in the gas phase.

  1. [Photonic Efficiency of Ethyl Acetate Photolysis in Gas Phase: Dependence on Wavelength and Catalyst]. (United States)

    Fang, Xue-hui; Zhao, Jie; Shu, Li; Gao, Yong; Ye, Zhao-lian


    Four kinds of excilamps with different wavelengths (XeCl*, KrCl*, XeBr* and KrBr*) were used for removing ethyl acetate in gas phase. The removal efficiencies of ethyl acetate by three loaded catalysts (TiO2 loaded on organic film, graphene loaded on organic film, and TiO2 loaded on mesh) were compared, and the effects of lamp sources, irradiation power and initial concentration on the removal efficiency were also investigated. Moreover, irradiation spectra and power of light sources were determined, and photonic efficiencies under different reaction conditions were calculated. The experimental results showed that the removal efficiency of ethyl acetate decreased in the order of KrBr* > KrCl* > XeCl* > XeBr*, while the photonic efficiency seemed to be relatively high with both XeCl* and KrBr* excilamps. In the presence of the catalyst of TiO2 loaded on organic film, both the removal efficiency and the photonic efficiency were higher than those without catalyst, but the increment was not significant. The photonic efficiency increased with increasing initial concentration and gas flow rate. With KrBr* excilamp, a photonic efficiency of 5.63% was obtained when the experimental conditions were set as: irradiation power of 0.76 W, initial concentration of 946 mg x m(-3), and gas flow rate of 600 mL x min(-1).

  2. Phase field theory modeling of methane fluxes from exposed natural gas hydrate reservoirs (United States)

    Kivelä, Pilvi-Helinä; Baig, Khuram; Qasim, Muhammad; Kvamme, Bjørn


    Fluxes of methane from offshore natural gas hydrate into the oceans vary in intensity from massive bubble columns of natural gas all the way down to fluxes which are not visible within human eye resolution. The driving force for these fluxes is that methane hydrate is not stable towards nether minerals nor towards under saturated water. As such fluxes of methane from deep below hydrates zones may diffuse through fluid channels separating the hydrates from minerals surfaces and reach the seafloor. Additional hydrate fluxes from hydrates dissociating towards under saturated water will have different characteristics depending on the level of dynamics in the actual reservoirs. If the kinetic rate of hydrate dissociation is smaller than the mass transport rate of distributing released gas into the surrounding water through diffusion then hydrodynamics of bubble formation is not an issue and Phase Field Theory (PFT) simulations without hydrodynamics is expected to be adequate [1, 2]. In this work we present simulated results corresponding to thermodynamic conditions from a hydrate field offshore Norway and discuss these results with in situ observations. Observed fluxes are lower than what can be expected from hydrate dissociating and molecularly diffusing into the surrounding water. The PFT model was modified to account for the hydrodynamics. The modified model gave higher fluxes, but still lower than the observed in situ fluxes.

  3. Reactions between M+ (M = Si, Ge, Sn and Pb) and benzene in the gas phase. (United States)

    Xing, Xiaopeng; Tian, Zhixin; Liu, Hongtao; Tang, Zichao


    Using a laser ablation/inert buffer gas ion source coupled with a reflectron time-of-flight mass spectrometer, the gas-phase reactions between the IVA group element ions M(+) (M = Si, Ge, Sn and Pb) and benzene seeded in argon gas were studied. In addition to the association reaction pathway (forming [M(C(6)H(6))(x)](+), x = 1, 2, etc.), benzene was dissociated to form complex ions [M(C(5)H(5))](+), [M(C(7)H(5))](+) and [M(C(9)H(x))](+) (x = 5, 7 and 9), etc. DFT theoretical calculations indicated that, in the association products [M(C(6)H(6))](+), the M atom is close to one carbon atom of benzene, while in most of the dissociation complexes, pentagonal structures (M/cyclopentadienyl derivatives) were formed, with the M atom situated near the fivefold axis of the five-membered ring. The bond patterns in these complexes are discussed. Copyright 2003 John Wiley & Sons, Ltd.

  4. Gas Phase Pressure Effects on the Apparent Thermal Conductivity of JSC-1A Lunar Regolith Simulant (United States)

    Yuan, Zeng-Guang; Kleinhenz, Julie E.


    Gas phase pressure effects on the apparent thermal conductivity of a JSC-1A/air mixture have been experimentally investigated under steady state thermal conditions from 10 kPa to 100 kPa. The result showed that apparent thermal conductivity of the JSC-1A/air mixture decreased when pressure was lowered to 80 kPa. At 10 kPa, the conductivity decreased to 0.145 W/m/degree C, which is significantly lower than 0.196 W/m/degree C at 100 kPa. This finding is consistent with the results of previous researchers. The reduction of the apparent thermal conductivity at low pressures is ascribed to the Knudsen effect. Since the characteristic length of the void space in bulk JSC-1A varies over a wide range, both the Knudsen regime and continuum regime can coexist in the pore space. The volume ratio of the two regimes varies with pressure. Thus, as gas pressure decreases, the gas volume controlled by Knudsen regime increases. Under Knudsen regime the resistance to the heat flow is higher than that in the continuum regime, resulting in the observed pressure dependency of the apparent thermal conductivity.

  5. Gas and particle phase chemical characterization of photochemical smog in Beijing and Hong Kong (United States)

    Hallquist, Mattias; Le Breton, Michael; Guo, Song; Zhen Yu, Jian; Hallquist, Åsa. M.; Pathak, Ravi K.; Liu, Qianyun; Wang, Yuchen; Li, Jinjian; Chan, Chak K.; Wang, Yujue; Zheng, Jing; Yang, Yudong; Lu, Keding; Wu, Zhijun; Hu, Min


    Secondary chemistry transforming primary pollutants is of high relevance for Chinese photochemical smog. In particular, formation of ozone (O3) and particulate matter (PM), including Secondary Organic Aerosols (SOA), are of major concern regarding impacts on health, climate and ecosystems. The atmospheric oxidation processes leading to SOA formation are complex and involves thousands of different compounds, both of biogenic and anthropogenic origin. Furthermore, for a thorough understanding both the gas and the particle phase need to be considered. As part of an intercollaborative project to assess the photochemical smog in China, two major field campaigns were arranged in 2016; in Changping, Bejing during springtime and at HKUST, Hong Kong during the autumn. Alongside with other advanced instrumentations, a Time of Flight Chemical Ionisation Mass Spectrometer (ToF CIMS) utilising the Filiter Inlet for Gases and AEROsols (FIGAERO) was used to chemically characterize the gas and the particle phase. This specific instrument applies soft ionization limiting the fragmentation and one can usually identify molecular composition of hundreds of different parent molecules. In both Beijing and Hong Kong the iodide ionization scheme was utilised, making it possible to specifically detect oxygenated compounds such as carboxylic acids, organic nitrates and sulphates as well as some inorganic compounds e.g. N2O5, ClNO2, and HONO. For numerous compounds significant levels were detected in both the gas and particle phase enabling evaluation of partitioning and gas-to-particle transformation and its relationship to atmospheric conditions and estimated vapour pressures. Furthermore, the detection of molecular markers such as levoglucosan, C6H5NO3, C10H16NSO7, C5H8SO7, C5H8O4 can support source apportionment and atmospheric process description. In order to further investigate atmospheric ageing/processing a portable laminar flow reactor (Go:PAM) was for selected periods utilized to

  6. Moisture effects on greenhouse gases generation in nitrifying gas-phase compost biofilters. (United States)

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


    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

  7. Synergistic effects of liquid and gas phase discharges using pulsed high voltage for dyes degradation in the presence of oxygen. (United States)

    Yang, Bin; Zhou, Minghua; Lei, Lecheng


    The technology of combined liquid and gas phase discharges (LGD) using pulsed high voltage for dyes degradation was developed in this study. Apparent synergistic effects for Acid orange II (AO) degradation in the presence of oxygen were observed. The enhancement of AO degradation rate was around 302%. Furthermore, higher energy efficiency was obtained comparing with individual liquid phase discharge (LD) or gas phase discharge process (GD). The AO degradation in the presence of oxygen by LGD proceeded through the direct ozone oxidation and the ozone decomposition induced by LD. Important operating parameters such as electrode distance, applied voltage, pulse repetition rate, and types of dyes were further investigated.

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

    KAUST Repository

    Hong, Jongsup


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

  9. The influence of gas phase velocity fluctuations on primary atomization and droplet deformation (United States)

    Kourmatzis, A.; Masri, A. R.


    The effects of grid-generated velocity fluctuations on the primary atomization and subsequent droplet deformation of a range of laminar liquid jets are examined using microscopic high-speed backlit imaging of the break-up zone and laser Doppler anemometry of the gas phase separately. This is done for fixed gas mean flow conditions in a miniature wind tunnel experiment utilizing a selection of fuels, turbulence-generating grids and two syringe sizes. The constant mean flow allows for an isolated study of velocity fluctuation effects on primary atomization in a close approximation to homogeneous decaying turbulence. The qualitative morphology of the primary break-up region is examined over a range of turbulence intensities, and spectral analysis is performed in order to ascertain the break-up frequency which, for a case of no grid, compares well with the existing literature. The addition of velocity fluctuations tends to randomize the break-up process. Slightly downstream of the break-up region, image processing is conducted in order to extract a number of metrics, which do not depend on droplet sphericity, and these include droplet aspect ratio and orientation, the latter quantity being somewhat unconventional in spray characterization. A turbulent Weber number which takes into account gas phase fluctuations is utilized to characterize the resulting droplet shapes, in addition to a mean Weber number . Above a a clear positive relationship exists between the mean aspect ratio of droplets and the turbulent Weber number where is varied by altering all relevant variables including the velocity root mean square, the initial droplet diameter, the surface tension and the density.

  10. PAHs levels in gas and particle-bound phase in schools at different locations in Serbia

    Directory of Open Access Journals (Sweden)

    Živković Marija


    Full Text Available This study investigated seasonal variation of PAHs and their partition between gas and particulate-bounded phases in indoor and outdoor air in 4 schools in Serbia located at different locations. The sampling campaigns were conducted during one workweek at each school successively. Campaigns were conducted in schools during heating and non-heating seasons in December 2011 and June 2012. Seasonal variations of gas and particle-bounded PAHs concentrations were observed with higher levels during heating season. The highest total PAH values were associated with the gas phase in both sampling periods. The total PAHs concentration at indoor and at the outdoor sites, during heating season, ranged from 88.45 to 447.72 ng/m3 and 201.69 to 1017.15 ng/m3, respectively. During non-heating season, the total PAHs concentration ranged from 36.91 to 271.57 ng/m3 in indoor environment and 27.00 to 132.32 ng/m3 in outdoor environment. Most of the I/O ratios were less than 1, which indicated that the indoor PAHs were mostly from outdoor sources. The use of diagnostic ratio showed that traffic emission and coal combustion are the major sources of PAHs. Only the diagnostic ratios for the school, located near the industrial area, showed significant deviation compared to other schools. [Projekat Ministarstva nauke Republike Srbije, br. TR33036: Development of new meteorological mast for turbulence parameters characterization and br. III42008: Evaluation of Energy Performances and Indoor Environment Quality of Educational Buildings in Serbia with Impact to Health

  11. Experimental and CFD Simulations of Vertical Two-Phase Slug Flow for Gas-Newtonian and Non-Newtonian Liquids

    DEFF Research Database (Denmark)

    Ratkovich, Nicolas Rios; Bentzen, Thomas Ruby; Majumder, S.

    Gas-liquid two-phase flows are presented everywhere in industrial processes (i.e. gas-oil pipelines). In spite of the common occurrence of these two-phase flows, their understanding is limited compared to single-phase flows. Different studies on two-phase flow have focus on developing empirical...... correlations based on large sets of experiment data for void fraction [1,2] and pressure drop [3,4] which have proven to be accurate for the specific condition that their where developed for. Currently, dozens of void fraction and pressure drop correlations for different flow patterns are available...... in the literature but none of them is enough robust and suitable for different conditions (i.e. flow patterns, gas-liquid combinations, pipe inclination angles, etc.). This clearly represents a drawback and more research in required on this field....

  12. Preparation of cold ions in strong magnetic field and its application to gas-phase NMR spectroscopy

    International Nuclear Information System (INIS)

    Fuke, K.; Ohshima, Y.; Tona, M.


    Nuclear Magnetic Resonance (NMR) technique is widely used as a powerful tool to study the physical and chemical properties of materials. However, this technique is limited to the materials in condensed phases. To extend this technique to the gas-phase molecular ions, we are developing a gas-phase NMR apparatus. In this note, we describe the basic principle of the NMR detection for molecular ions in the gas phase based on a Stern-Gerlach type experiment in a Penning trap and outline the apparatus under development. We also present the experimental procedures and the results on the formation and the manipulation of cold ions under a strong magnetic field, which are the key techniques to detect the NMR by the present method

  13. Glass bottle sampling solid phase microextraction gas chromatography mass spectrometry for breath analysis of drug metabolites. (United States)

    Lu, Yan; Niu, Wenqi; Zou, Xue; Shen, Chengyin; Xia, Lei; Huang, Chaoqun; Wang, Hongzhi; Jiang, Haihe; Chu, Yannan


    Breath analysis is a non-invasive approach which may be applied to disease diagnosis and pharmacokinetic study. In the case of offline analysis, the exhaled gas needs to be collected and the sampling bag is often used as the storage vessel. However, the sampling bag usually releases some extra compounds, which may interfere with the result of the breath test. In this study, a novel breath sampling glass bottle was developed with a syringe needle sampling port for solid phase microextraction (SPME). Such a glass bottle scarcely liberates compounds and can be used to collect exhaled gas for ensuing analysis by gas chromatography-mass spectrometry (GC-MS). The glass bottle sampling SPME-GC-MS analysis was carried out to investigate the breath metabolites of myrtol, a multicompound drug normally used in the treatment of bronchitis and sinusitis. Four compounds, α-pinene, 2,3-dehydro-1,8-cineole, d-limonene and 1,8-cineole were found in the exhaled breath of all eight volunteers who had taken the myrtol. While for other ten subjects who had not used the myrtol, these compounds were undetectable. In the SPME-GC-MS analysis of the headspace of myrtol, three compounds were detected including α-pinene, d-limonene and 1,8-cineole. Comparing the results of breath and headspace analysis, it indicates that 2,3-dehydro-1,8-cineole in the breath is the metabolite of 1,8-cineole. It is the first time that this metabolite was identified in human breath. The study demonstrates that the glass bottle sampling SPME-GC-MS method is applicable to exhaled gas analysis including breath metabolites investigation of drugs like myrtol. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Gas dispersion and bubble-to-emulsion phase mass exchange in a gas-solid bubbling fluidized bed: a computational and experimental study

    NARCIS (Netherlands)

    Patil, D.J.; van Sint Annaland, M.; Kuipers, J.A.M.


    Knowledge of gas dispersion and mass exchange between the bubble and the emulsion phases is essential for a correct prediction of the performance of fluidized beds, particularly when catalytic reactions take place. Test cases of single rising bubble and a bubbling fluidized bed operated with a jet

  15. A protocol for detecting and scavenging gas-phase free radicals in mainstream cigarette smoke. (United States)

    Yu, Long-Xi; Dzikovski, Boris G; Freed, Jack H


    Cigarette smoking is associated with human cancers. It has been reported that most of the lung cancer deaths are caused by cigarette smoking (5,6,7,12). Although tobacco tars and related products in the particle phase of cigarette smoke are major causes of carcinogenic and mutagenic related diseases, cigarette smoke contains significant amounts of free radicals that are also considered as an important group of carcinogens(9,10). Free radicals attack cell constituents by damaging protein structure, lipids and DNA sequences and increase the risks of developing various types of cancers. Inhaled radicals produce adducts that contribute to many of the negative health effects of tobacco smoke in the lung(3). Studies have been conducted to reduce free radicals in cigarette smoke to decrease risks of the smoking-induced damage. It has been reported that haemoglobin and heme-containing compounds could partially scavenge nitric oxide, reactive oxidants and carcinogenic volatile nitrosocompounds of cigarette smoke(4). A 'bio-filter' consisted of haemoglobin and activated carbon was used to scavenge the free radicals and to remove up to 90% of the free radicals from cigarette smoke(14). However, due to the cost-ineffectiveness, it has not been successfully commercialized. Another study showed good scavenging efficiency of shikonin, a component of Chinese herbal medicine(8). In the present study, we report a protocol for introducing common natural antioxidant extracts into the cigarette filter for scavenging gas phase free radicals in cigarette smoke and measurement of the scavenge effect on gas phase free radicals in mainstream cigarette smoke (MCS) using spin-trapping Electron Spin Resonance (ESR) Spectroscopy(1,2,14). We showed high scavenging capacity of lycopene and grape seed extract which could point to their future application in cigarette filters. An important advantage of these prospective scavengers is that they can be obtained in large quantities from byproducts of

  16. Photocatalytic degradation of 2-phenethyl-2-chloroethyl sulfide in liquid and gas phases. (United States)

    Vorontsov, Alexandre V; Panchenko, Alexander A; Savinov, Evgueni N; Lion, Claude; Smirniotis, Panagiotis G


    This work explores the ability of photocatalysis to decontaminate water and air from chemical warfare agent mustard using its simulant 2-phenethyl 2-chloroethyl sulfide (PECES). PECES like mustard slowly dissolves in water with hydrolysis, forming 2-phenethyl 2-hydroxyethyl sulfide (PEHES). Irradiation of TiO2 suspension containing PECES with the unfiltered light of a mercury lamp (lambda > or = 254 nm) decomposed all PECES mostly via photolysis. Reaction under filtered light (lambda > 300 nm) proceeds mainly photocatalytically and requires longer time. Sulfur from starting PECES is completely transformed into sulfuric acid at the end of the reaction. Detected volatile, nonvolatile, surface products, and the suggested scheme of degradation are reported. The main volatile products are styrene and benzaldehyde, nonvolatile--hydroxylated PEHES, surface--2-phenethyl disulfide. Photolysis of PECES produced the same set of volatile products as photocatalysis. Photocatalytic degradation of gaseous PECES in air results in its mineralization but is accompanied by TiO2 deactivation. The highest rate of mineralization with minimum deactivation was observed at about room temperature and a water concentration of 27,500 ppm. No gaseous products except CO2 were detected. The main extracted surface product was styrene. It was concluded that PECES photocatalytic degradation proceeds mainly via C-S bond cleavage and further oxidation of the products. Hydrolysis of the C-S bond was detected only in gas-phase photocatalytic degradation. The quantum efficiency of gas-phase degradation (0.28%) was much higher than that of liquid-phase degradation (0.008%). The results demonstrate the ability of photocatalysis to decontaminate an aqueous and especially an air environment

  17. Adsorption of silane films on iron surfaces: Characterization of films and development of novel silane-based pretreatments to replace chromates and phosphates (United States)

    Zhang, Chunbin

    This work mainly consists of three parts. The first part deals with characterization of silane films on metal surfaces (iron) by various analytical techniques. The second part describes the development of novel silane-based pretreatments of cold rolled steel (CRS) which may be used for the replacement of pretreatments based on phosphating with chromating as a final rinse. The third part focuses on the corrosion performance of polyurethane-power-paint-coated CRS panels by means of electrochemical impedance spectroscopy. In the first part of this work, films deposited on polished iron surfaces from solutions of gamma-aminopropyltriethoxysilane (gamma-APS), 1,2-bis(triethoxysilyl) ethane (BTSE), their mixtures, and other silanes were characterized by means of ellipsometry, Reflection-Absorption Infrared Spectroscopy, Time-of-Flight Secondary Ion Mass Spectrometry, and etc. The purpose of the second part of this work was to develop novel silane-based pretreatments that can replace the commercially used phosphating pretreatment with a chromate final rinse for CRS for the benefit of a cleaner environment. The corrosion performance of the coated CRS panels was studied by means of a cyclic corrosion test and the standard ASTM salt spray test B117. A novel silane-based pretreatment, namely, a two step silane treatment, which used two silanes, one organofunctional silane (gamma-APS) and one non-functional silane (BTSE), was developed. Results obtained from cyclic corrosion and salt spray tests showed that the two step silane treatment provided corrosion performance for CRS panels equal to the commercially used iron phosphating pretreatment with a chromate final rinse. In the third part of this work, electrochemical impedance spectroscopy (EIS) was employed to study the corrosion performance of CRS panels that were coated with polyurethane powder paint. The purpose was to study the effects of various pretreatments and pH on the performance of the paint-CRS systems during

  18. Exploitation of a microporous organic polymer as a stationary phase for capillary gas chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Cuiming; Liu, Shuqin; Xu, Jianqiao; Ding, Yajuan; Ouyang, Gangfeng, E-mail:


    Microporous organic polymers (MOPs) have emerged as a new class of functional porous materials with unique characteristics and potential uses in diverse areas. However, the field of MOPs for gas chromatographic (GC) separations has not been well explored. Herein, a MOP namely KAPs-1 was dynamic coated onto a capillary column for the first time. The fabricated column exhibited a nonpolar nature and the column efficiency for n-dodecane was up to 7769 plates m{sup −1}. The KAPs-1 coated column showed high GC separation performance for a series of volatile organic compounds (VOCs) including the challenging ethylbenzene and xylene isomers, which could not be resolved at baseline on the commercial 5% phenyl polysiloxane stationary phase. Moreover, the relative standard deviations for five replicate determinations of the studied analytes were 0.0–0.6%, 0.9–3.2%, 1.1–5.9%, 0.8–3.7% for retention time, peak area, peak height and peak width, respectively. To investigate the interaction between some analytes and the stationary phase, thermodynamic and kinetic parameters were also evaluated. The results of this study show it is very promising to utilize MOPs as stationary phases for capillary GC. - Highlights: • A microporous organic polymer was explored as a novel stationary phase for capillary GC. • The column showed high separation performance for VOCs including the challenging ethylbenzene and xylene isomers. • Thermodynamic and kinetic parameters for BTEXs were determined to study the analyte-stationary phase interaction.

  19. Exploitation of a microporous organic polymer as a stationary phase for capillary gas chromatography

    International Nuclear Information System (INIS)

    Lu, Cuiming; Liu, Shuqin; Xu, Jianqiao; Ding, Yajuan; Ouyang, Gangfeng


    Microporous organic polymers (MOPs) have emerged as a new class of functional porous materials with unique characteristics and potential uses in diverse areas. However, the field of MOPs for gas chromatographic (GC) separations has not been well explored. Herein, a MOP namely KAPs-1 was dynamic coated onto a capillary column for the first time. The fabricated column exhibited a nonpolar nature and the column efficiency for n-dodecane was up to 7769 plates m −1 . The KAPs-1 coated column showed high GC separation performance for a series of volatile organic compounds (VOCs) including the challenging ethylbenzene and xylene isomers, which could not be resolved at baseline on the commercial 5% phenyl polysiloxane stationary phase. Moreover, the relative standard deviations for five replicate determinations of the studied analytes were 0.0–0.6%, 0.9–3.2%, 1.1–5.9%, 0.8–3.7% for retention time, peak area, peak height and peak width, respectively. To investigate the interaction between some analytes and the stationary phase, thermodynamic and kinetic parameters were also evaluated. The results of this study show it is very promising to utilize MOPs as stationary phases for capillary GC. - Highlights: • A microporous organic polymer was explored as a novel stationary phase for capillary GC. • The column showed high separation performance for VOCs including the challenging ethylbenzene and xylene isomers. • Thermodynamic and kinetic parameters for BTEXs were determined to study the analyte-stationary phase interaction.

  20. Impact of improved technology on industrial greenhouse-gas emissions in developing countries. Phase 1

    International Nuclear Information System (INIS)


    In response to a formal request by the Group of 77 and China, the United Nations Industrial Development Organization (UNIDO) initiated a study to identify opportunities to reduce the emissions of greenhouse gases from energy-intensive industries in developing countries. These sectors currently include iron and steel, petroleum refining, cement, paper and pulp and nitrogen fertilizers. The aim of this first phase was to describe: how energy is used in the energy-intensive industries in developing countries today; what current trends indicate for the future; the potential contribution of improved technologies and practices to moving toward more sustainable industrial production in developing countries, and to provide developing countries with an analytical tool for evaluating opportunities to limit industrial greenhouse-gas (GHG) emissions in their industrial sectors through the transfer of improved technologies and processes. The immediate objectives of Phase 1 were twofold: to provide information to developing countries in the form of an inventory of energy-efficient, best-available technologies and processes that can be used to abate greenhouse-gas emissions in the most energy-intensive industrial sub-sectors as well as cross-cutting measures applicable in a range of sub-sectors, and; to provide an analytical methodology in the form of a software tool that enables the user to evaluate and compare the costs, energy requirements, and greenhouse-gas emissions associated with scenarios of specific technology and process options. To meet these objectives, the first phase of the study comprised: a Report entitled Industrial Greenhouse-gas Emissions from Developing Countries; a Software Package containing, an Industrial Technology Inventory, and an Analysis Tool, and; Industry/country-specific Case Studies. The Report describes current energy use and greenhouse-gas emissions in energy-intensive industries in developing countries, and similar industries exemplifying good

  1. Gas-phase laser synthesis of aggregation-free, size-controlled hydroxyapatite nanoparticles

    International Nuclear Information System (INIS)

    Bapat, Parimal V.; Kraft, Rebecca; Camata, Renato P.


    Nanophase hydroxyapatite (HA) is finding applications in many areas of biomedical research, including bone tissue engineering, drug delivery, and intracellular imaging. Details in chemical composition, crystal phase makeup, size, and shape of HA nanoparticles play important roles in achieving the favorable biological responses required in these applications. Most of the nanophase HA synthesis techniques involve solution-based methods that exhibit substantial aggregation of particles upon precipitation. Typically these methods also have limited control over the particle size and crystal phase composition. In this study, we describe the gas-phase synthesis of aggregation-free, size-controlled HA nanoparticles with mean size in the 20–70 nm range using laser ablation followed by aerosol electrical mobility classification. Nanoparticle deposits with adjustable number concentration were obtained on solid substrates. Particles were characterized by transmission electron microscopy, atomic force microscopy, and X-ray diffraction. Samples are well represented by log-normal size distributions with geometric standard deviation σ g ≈ 1.2. The most suitable conditions for HA nanoparticle formation at a laser fluence of 5 J/cm 2 were found to be a temperature of 800 °C and a partial pressure of water of 160 mbar.

  2. Exploitation of a microporous organic polymer as a stationary phase for capillary gas chromatography. (United States)

    Lu, Cuiming; Liu, Shuqin; Xu, Jianqiao; Ding, Yajuan; Ouyang, Gangfeng


    Microporous organic polymers (MOPs) have emerged as a new class of functional porous materials with unique characteristics and potential uses in diverse areas. However, the field of MOPs for gas chromatographic (GC) separations has not been well explored. Herein, a MOP namely KAPs-1 was dynamic coated onto a capillary column for the first time. The fabricated column exhibited a nonpolar nature and the column efficiency for n-dodecane was up to 7769 plates m(-1). The KAPs-1 coated column showed high GC separation performance for a series of volatile organic compounds (VOCs) including the challenging ethylbenzene and xylene isomers, which could not be resolved at baseline on the commercial 5% phenyl polysiloxane stationary phase. Moreover, the relative standard deviations for five replicate determinations of the studied analytes were 0.0-0.6%, 0.9-3.2%, 1.1-5.9%, 0.8-3.7% for retention time, peak area, peak height and peak width, respectively. To investigate the interaction between some analytes and the stationary phase, thermodynamic and kinetic parameters were also evaluated. The results of this study show it is very promising to utilize MOPs as stationary phases for capillary GC. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Gas-liquid Phase Distribution and Void Fraction Measurements Using the MRI (United States)

    Daidzic, N. E.; Schmidt, E.; Hasan, M. M.; Altobelli, S.


    We used a permanent-magnet MRI system to estimate the integral and spatially- and/or temporally-resolved void-fraction distributions and flow patterns in gas-liquid two-phase flows. Air was introduced at the bottom of the stagnant liquid column using an accurate and programmable syringe pump. Air flow rates were varied between 1 and 200 ml/min. The cylindrical non-conducting test tube in which two-phase flow was measured was placed in a 2.67 kGauss MRI with MRT spectrometer/imager. Roughly linear relationship has been obtained for the integral void-fraction, obtained by volume-averaging of the spatially-resolved signals, and the air flow rate in upward direction. The time-averaged spatially-resolved void fraction has also been obtained for the quasi-steady flow of air in a stagnant liquid column. No great accuracy is claimed as this was an exploratory proof-of-concept type of experiment. Preliminary results show that MRI a non-invasive and non-intrusive experimental technique can indeed provide a wealth of different qualitative and quantitative data and is especially well suited for averaged transport processes in adiabatic and diabatic multi-phase and/or multi-component flows.

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

    International Nuclear Information System (INIS)

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


    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

  5. Graphitic carbon nitride as high-resolution stationary phase for gas chromatographic separations. (United States)

    Zheng, Yunzhong; Qi, Meiling; Fu, Ruonong


    This work presents the first example of utilization of graphitic carbon nitride (g-C3N4) as stationary phase for capillary gas chromatographic (GC) separations. The statically coated g-C3N4 column showed the column efficiencies of 3760 plates/m and weak polarity. Its resolving capability and retention behaviours were investigated by using the Grob test mixture, and mixtures of diverse types of analytes, and structural and positional isomers. The results showed superior separation performance of the g-C3N4 stationary phase for some critical analytes and preferential retention for aromatic analytes. Specifically, it exhibited high-resolution capability for aromatic and aliphatic isomers such as methylnaphthalenes and dimethylnaphthalenes, phenanthrene and anthracene and alkane isomers. In addition, g-C3N4 column showed excellent thermal stability up to 280°C and good repeatability with relative standard deviation (RSD) values less than 0.09% for intra-day, below 0.23% for inter-day and in the range of 1.9-8.4% for between-column, respectively. The advantageous separation performance shows the potential of g-C3N4 and related materials as stationary phase in GC and other separation technologies. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Using artificial intelligence to improve identification of nanofluid gas-liquid two-phase flow pattern in mini-channel (United States)

    Xiao, Jian; Luo, Xiaoping; Feng, Zhenfei; Zhang, Jinxin


    This work combines fuzzy logic and a support vector machine (SVM) with a principal component analysis (PCA) to create an artificial-intelligence system that identifies nanofluid gas-liquid two-phase flow states in a vertical mini-channel. Flow-pattern recognition requires finding the operational details of the process and doing computer simulations and image processing can be used to automate the description of flow patterns in nanofluid gas-liquid two-phase flow. This work uses fuzzy logic and a SVM with PCA to improve the accuracy with which the flow pattern of a nanofluid gas-liquid two-phase flow is identified. To acquire images of nanofluid gas-liquid two-phase flow patterns of flow boiling, a high-speed digital camera was used to record four different types of flow-pattern images, namely annular flow, bubbly flow, churn flow, and slug flow. The textural features extracted by processing the images of nanofluid gas-liquid two-phase flow patterns are used as inputs to various identification schemes such as fuzzy logic, SVM, and SVM with PCA to identify the type of flow pattern. The results indicate that the SVM with reduced characteristics of PCA provides the best identification accuracy and requires less calculation time than the other two schemes. The data reported herein should be very useful for the design and operation of industrial applications.

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

    International Nuclear Information System (INIS)

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


    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.

  8. The structures of tellurium(IV) halides in the gas phase and as solvated molecules. (United States)

    Shlykov, Sergey A; Giricheva, Nina I; Titov, Anton V; Szwak, Małgorzata; Lentz, Dieter; Girichev, Georgiy V


    The structures of molecular tellurium tetrafluoride and tellurium tetrachloride were determined by a combination of gas-phase electron diffraction, mass spectrometry and quantum chemical calculations. The combined GED/MS experiments showed no evidence of decomposition of TeF(4) and TeCl(4). No ions of oligomeric (dimeric, trimeric, etc.) or any other composition were found in the mass spectra. The monomeric molecules possess a pseudo trigonal bipyramidal structure (C(2v) symmetry) with the equatorial Te-X distances being shorter than the axial ones. The fluorine atoms are bent away from the lone pair resulting in X(eq)-Te-X(eq) and X(eq)-Te-X(ax) bond angles smaller than 120 and 90 degrees, respectively. The structure of solvates TeF(4) (THF)(2), TeF(4) (dioxane) TeF(4) (DME)(2), TeF(4)(Et(2)O) TeF(4)(toluene), TeCl(4)(CH(3)CN)(2), TeCl(4)(DME)(2) and TeCl(4)(dioxane) were determined by X-ray diffraction. The structures of tellurium tetrafluoride solvates are strongly influenced by the choice of the solvent molecules. Monomeric TeF(4) units were obtained with THF, DME and dioxane whereas fluoride bridged coordination polymers were formed using diethyl ether or toluene. All tellurium tetrachloride solvates studied contain monomeric TeCl(4) units with coordinated solvent molecules. Coordination numbers range from four in the gas phase to eight in the TeF(4) dimethoxyethane solvate. Geometric parameters of the TeX(4) molecules in the crystal, solvates and gas phase were compared. DFT, MP2, CCSD, CCSD(T) methods were applied for calculation of geometric and vibrational characteristics of free TeX(4) molecules (X = F, Cl). The pseudorotation barriers were estimated and an NBO analysis was performed. It was shown that both, GED and theoretical, quantitative results are in agreement with the qualitative results of the VSEPR model.

  9. Characterization of two-phase mixture (petroleum, salted water or gas) by gamma radiation transmission

    International Nuclear Information System (INIS)

    Eichlt, Jair Romeu


    A mathematical description was accomplished to determine the discrimination of a substance in a two-phase mixture, for one beam system, using the five energy lines (13.9, 17.8,26.35 and 59,54 keV) of the 241 Am source. The mathematical description was also accomplished to determine the discrimination of two substances in a three-phase mixture, for a double beam system.. he simulated mixtures for the one beam system were petroleum/salted water or gas. The materials considered in these simulations were: four oils types, denominated as A, B, Bell and Generic, one kind of natural gas and salted water with the following salinities: 35.5, 50, 100, 150, 200, 250 and 300 kg/m 3 of Na Cl. The simulation for the one beam system consisted of a box with acrylic walls and other situation with a box of epoxi walls reinforced with fiber of carbon. The epoxi with carbon fiber was used mainly due to the fact that this material offers little attenuation to the fotons and it resists great pressures. With the results of the simulations it was calculated tables of minimum discrimination for each possible two-phase mixture with petroleum, gas and salted water at several salinities. These discrimination tables are the theoretical forecasts for experimental measurements, since they supply the minimum mensurable percentage for each energy line, as well as the ideal energy for the measurement of each mixture, or situation. The simulated discrimination levels were tested employing experimental arrangements with conditions and materials similar to those of the simulations, for the case of box with epoxi wall reinforced with carbon fiber, at the energies of 20.8 and 59.54 keV. It was obtained good results. For example, for the mixture of salted water (35.5 kg/m 3 ) in paraffin (simulating the petroleum), it was obtained an experimental discrimination minimum of 10% of salted water for error statistics of 5% in I and I o , while the theoretical simulation foresaw the same discrimination level

  10. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Xiaobing, E-mail: [Department of Chemistry, University of York, Heslington, York, YO10 5DD (United Kingdom); Lewis, Alastair C., E-mail: [National Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD (United Kingdom)


    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 {mu}g cigarette{sup -1} ({mu}g cig{sup -1}) and the particulate carbonyl emissions varied in the range of 23-127 {mu}g cig{sup -1}. Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 {mu}g cig{sup -1} gaseous and 141 {mu}g cig{sup -1} particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: {yields} Carbonyl

  11. Nitric oxide gas phase release in human small airway epithelial cells

    Directory of Open Access Journals (Sweden)

    Suresh Vinod


    Full Text Available Abstract Background Asthma is a chronic airway inflammatory disease characterized by an imbalance in both Th1 and Th2 cytokines. Exhaled nitric oxide (NO is elevated in asthma, and is a potentially useful non-invasive marker of airway inflammation. However, the origin and underlying mechanisms of intersubject variability of exhaled NO are not yet fully understood. We have previously described NO gas phase release from normal human bronchial epithelial cells (NHBEs, tracheal origin. However, smaller airways are the major site of morbidity in asthma. We hypothesized that IL-13 or cytomix (IL-1β, TNF-α, and IFN-γ stimulation of differentiated small airway epithelial cells (SAECs, generation 10–12 and A549 cells (model cell line of alveolar type II cells in culture would enhance NO gas phase release. Methods Confluent monolayers of SAECs and A549 cells were cultured in Transwell plates and SAECs were allowed to differentiate into ciliated and mucus producing cells at an air-liquid interface. The cells were then stimulated with IL-13 (10 ng/mL or cytomix (10 ng/mL for each cytokine. Gas phase NO release in the headspace air over the cells was measured for 48 hours using a chemiluminescence analyzer. Results In contrast to our previous result in NHBE, baseline NO release from SAECs and A549 is negligible. However, NO release is significantly increased by cytomix (0.51 ± 0.18 and 0.29 ± 0.20, respectively reaching a peak at approximately 10 hours. iNOS protein expression increases in a consistent pattern both temporally and in magnitude. In contrast, IL-13 only modestly increases NO release in SAECs reaching a peak (0.06 ± 0.03 more slowly (30 to 48 hours, and does not alter NO release in A549 cells. Conclusion We conclude that the airway epithelium is a probable source of NO in the exhaled breath, and intersubject variability may be due, in part, to variability in the type (Th1 vs Th2 and location (large vs small airway

  12. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    International Nuclear Information System (INIS)

    Pang, Xiaobing; Lewis, Alastair C.


    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 μg cigarette -1 (μg cig -1 ) and the particulate carbonyl emissions varied in the range of 23-127 μg cig -1 . Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 μg cig -1 gaseous and 141 μg cig -1 particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: → Carbonyl emission factors in both gas (16 species) and

  13. Mechanistic aspects of silane coupling agents with different functionalities on reinforcement of silica-filled natural rubber compounds

    NARCIS (Netherlands)

    Kaewsakul, Wisut; Sahakaro, Kannika; Dierkes, Wilma K.; Noordermeer, Jacobus W.M.


    Silane coupling agents containing different specific functionalities are studied to gain understanding of their roles in silica-filled natural rubber (NR) compounds. Five different silane coupling agents, that is bis-(triethoxysilylpropyl) tetrasulfide (TESPT), bis-(triethoxysilylpropyl) disulfide

  14. A Robust Computational Method for Coupled Liquid-liquid Phase Separation and Gas-particle Partitioning Predictions of Multicomponent Aerosols (United States)

    Zuend, A.; Di Stefano, A.


    Providing efficient and reliable model predictions for the partitioning of atmospheric aerosol components between different phases (gas, liquids, solids) is a challenging problem. The partitioning of water, various semivolatile organic components, inorganic acids, bases, and salts, depends simultaneously on the chemical properties and interaction effects among all constituents of a gas + aerosol system. The effects of hygroscopic particle growth on the water contents and physical states of potentially two or more liquid and/or solid aerosol phases in turn may significantly affect multiphase chemistry, the direct effect of aerosols on climate, and the ability of specific particles to act as cloud condensation or ice nuclei. Considering the presence of a liquid-liquid phase separation in aerosol particles, which typically leads to one phase being enriched in rather hydrophobic compounds and the other phase enriched in water and dissolved electrolytes, adds a high degree of complexity to the goal of predicting the gas-particle partitioning of all components. Coupled gas-particle partitioning and phase separation methods are required to correctly account for the phase behaviour of aerosols exposed to varying environmental conditions, such as changes to relative humidity. We present new theoretical insights and a substantially improved algorithm for the reliable prediction of gas-particle partitioning at thermodynamic equilibrium based on the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. We introduce a new approach for the accurate prediction of the phase distribution of multiple inorganic ions between two liquid phases, constrained by charge balance, and the coupling of the liquid-liquid equilibrium model to a robust gas-particle partitioning algorithm. Such coupled models are useful for exploring the range of environmental conditions leading to complete or incomplete miscibility of aerosol constituents which will affect

  15. Decomposition of silane on tungsten or other materials (United States)

    Wiesmann, H.J.

    This invention relates to hydrogenated amorphous silicon produced by thermally decomposing silane (SiH/sub 4/) or other gases comprising H and Si, from a W or foil heated to a temperature of about 1400 to 1600/sup 0/C, in a vacuum of about 10-/sup 6/ to 10-/sup 4/ torr. A gaseous mixture is formed of atomic hydrogen and atomic silicon. The gaseous mixture is deposited onto a substrate independent of and outside the source of thermal decomposition. Hydrogenated amorphous silicon is formed. The presence of an ammonia atmosphere in the vacuum chamber enhances the photoconductivity of the hydrogenated amorphous silicon film.

  16. Biodesel Production from Pseudomonas Fluorescens Lp1 Lipase Immobilized on Amino-silane Modified Super Paramagnetic Fe3O4 Nanoparticles (United States)

    Kanimozhi, S.; Perinbam, K.


    An extracellular lipase from Pseudomonas fluorescens Lp1 isolated from oil contaminated soil was immobilized onto amino silane modified superparamagnetic Fe3O4 nanoparticles. The magnetic nanoparticles, magnetite was synthesized chemically by co-precipitation and characterized by Scanning Electron Microscopy (SEM), Fourier Transformed Infrared Spectroscopy (FT-IR) and Powder X-ray diffraction studies (XRD). The structure of the synthesized magnetic nanoparticles was uniform, spherical and the size was determined around 31 nm by powder XRD. The biodiesel production mixture was prepared by addition of waste cooking oil, lipase immobilized magnetite and methanol. The transesterified products were analyzed by Gas Liquid chromatography-Mass spectroscopy (GC-MS). The methyl esters such as Oxiraneundecanoic acid, 3-pentyl-methyl ester, Hexadecanoic acid, methyl ester and 10-Octadecenoic acid, methyl ester were obtained. The study experimentally proved the use of amino silane modified superparamagnetic Fe3O4 nanoparticles in biodiesel production from waste cooking oil.

  17. Biodesel Production from Pseudomonas Fluorescens Lp1 Lipase Immobilized on Amino-silane Modified Super Paramagnetic Fe3O4 Nanoparticles

    International Nuclear Information System (INIS)

    Kanimozhi, S; Perinbam, K


    An extracellular lipase from Pseudomonas fluorescens Lp1 isolated from oil contaminated soil was immobilized onto amino silane modified superparamagnetic Fe 3 O 4 nanoparticles. The magnetic nanoparticles, magnetite was synthesized chemically by co-precipitation and characterized by Scanning Electron Microscopy (SEM), Fourier Transformed Infrared Spectroscopy (FT-IR) and Powder X-ray diffraction studies (XRD). The structure of the synthesized magnetic nanoparticles was uniform, spherical and the size was determined around 31 nm by powder XRD. The biodiesel production mixture was prepared by addition of waste cooking oil, lipase immobilized magnetite and methanol. The transesterified products were analyzed by Gas Liquid chromatography-Mass spectroscopy (GC-MS). The methyl esters such as Oxiraneundecanoic acid, 3-pentyl-methyl ester, Hexadecanoic acid, methyl ester and 10-Octadecenoic acid, methyl ester were obtained. The study experimentally proved the use of amino silane modified superparamagnetic Fe 3 O 4 nanoparticles in biodiesel production from waste cooking oil.

  18. Effects of donor-acceptor electronic interactions on the rates of gas-phase metallocene electron-exchange reactions

    Energy Technology Data Exchange (ETDEWEB)

    Phelps, D.K.; Gord, J.R.; Freiser, B.S.; Weaver, M.J. (Purdue Univ., West Lafayette, IN (United States))


    Rate constants for electron self-exchange, k{sub ex}, of five cobaltocenium-cobaltocene and ferrocenium-ferrocene couples in the gas phase have been measured by means of Fourier transform ion cyclotron resonance mass spectrometry in order to explore the possible effects of donor-acceptor electronic coupling on gas-phase redox reactivity. The systems studied, Cp{sub 2}Co{sup +/0}, Cp{sub 2}Fe{sup +/0} (Cp = cyclopentadienyl), the decamethyl derivative Cp{prime}{sub 2}Fe{sup +/0}, carboxymethyl(cobaltocenium-cobaltocene) (Cp{sub 2}{sup e}Co{sup +/0}), and hydroxymethyl(ferrocenium-ferrocene) (HMFc{sup +/0}), were selected in view of the substantial variations in electronic coupling inferred on the basis of their solvent-dependent reactivities and theoretical grounds. The sequence of k{sub ex} values determined in the gas phase, Cp{sub 2}{sup e}Co{sup +/0} {approx} Cp{sub 2}Co{sup +/0} > Cp{prime}{sub 2}Fe{sup +/0} > HMFc{sup +/0} > Cp{sub 2}Fe{sup +/0}, is roughly similar to that observed in solution, although the magnitude (up to 5-fold) of the k{sub ex} variations is smaller in the former case. The likely origins of these differences in gas-phase reactivity are discussed in light of the known variations in the electronic coupling matrix element H{sub 12}, inner-shell reorganization energy {Delta}E*, and gas-phase ion-molecule interaction energy {Delta}E{sub w} extracted from solution-phase rates, structural data, and theoretical calculations. It is concluded that the observed variations in gas-phase k{sub ex} values, especially for Cp{sub 2}Fe{sup +/0} versus Cp{sub 2}Co{sup +/0}, arise predominantly from the presence of weaker donor-acceptor orbital overlap for the ferrocene couples, yielding inefficient electron tunneling for a substantial fraction of the gas-phase ion-molecule encounters. The anticipated differences as well as similarities of such nonadiabatic effects for gas-phase and solution electron-transfer processes are briefly outlined.

  19. A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions (United States)

    Conte, Marco; Wilson, Karen; Chechik, Victor


    A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X-band electron paramagnetic resonance spectroscopy.

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

    Energy Technology Data Exchange (ETDEWEB)

    Reisberg, L., E-mail: [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)


    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.