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Sample records for gas phase photocatalytic

  1. Gas-phase photocatalytic oxidation of acrylonitrile.

    PubMed

    Krichevskaya, Marina; Jõks, Svetlana; Kachina, Anna; Preis, Sergei

    2009-05-01

    Photocatalytic oxidation (PCO) of acrylonitrile (AN) on titanium dioxide in the gaseous phase was studied. AN readily undergoes photocatalytic degradation in a gas-solid system by using TiO(2) Degussa P25. The AN PCO volatile products, visible in the infrared spectra, included nitrogen dioxide, nitrous oxide, carbon dioxide, water, hydrogen cyanide and carbon monoxide. Longer contact time resulted in deeper oxidation of AN with decreasing hydrogen cyanide and increasing nitrogen dioxide content. The effect of temperature increasing from 60 to 130 degrees C was observed to be slightly negative in terms of AN degradation rate. However, the effect of increased temperature was noticeable in terms of the character and yields of the PCO products: HCN peaks diminished with growing peaks of NO(2). PMID:19424531

  2. Photocatalytic oxidation of gas-phase BTEX-contaminated waste streams

    SciTech Connect

    Gratson, D A; Nimlos, M R; Wolfrum, E J

    1995-03-01

    Researchers at the National Renewable Energy Laboratory (NREL) have been exploring heterogeneous photocatalytic oxidation (PCO) as a remediation technology for air streams contaminated with benzene, toluene, ethyl-benzene, and xylenes (BTEX). This research is a continuation of work performed on chlorinated organics. The photocatalytic oxidation of BTEX has been studied in the aqueous phase, however, a study by Turchi et al. showed a more economical system would involve stripping organic contaminants from the aqueous phase and treating the resulting gas stream. Another recent study by Turchi et al. indicated that PCO is cost competitive with such remediation technologies as activated carbon adsorption and catalytic incineration for some types of contaminated air streams. In this work we have examined the photocatalytic oxidation of benzene using ozone (0{sub 3}) as an additional oxidant. We varied the residence time in the PCO reactor, the initial concentration of the organic pollutant, and the initial ozone concentration in a single-pass reactor. Because aromatic hydrocarbons represent only a small fraction of the total hydrocarbons present in gasoline and other fuels, we also added octane to the reaction mixture to simulate the composition of air streams produced from soil-vapor-extraction or groundwater-stripping of sites contaminated with gasoline.

  3. Study of solid/gas phase photocatalytic reactions by electron ionization mass spectrometry.

    PubMed

    Nuño, Manuel; Ball, Richard J; Bowen, Chris R

    2014-08-01

    This paper describes a novel methodology for the real-time study of solid-gas phase photocatalytic reactions in situ. A novel reaction chamber has been designed and developed to facilitate the investigation of photoactive materials under different gas compositions. UV irradiation in the wavelength of ranges 376-387 and 381-392 nm was provided using specially designed high efficiency light emitting diode arrays. The experiments used air containing 190 ppm NO2 in a moist environment with a relative humidity of 0.1%. Photocatalytic samples consisting of pressed pellets of rutile and anatase crystalline forms of TiO2 were monitored over a period of 150 min. An ultra-high vacuum right angled bleed valve allowed a controlled flow of gas from the main reaction chamber at atmospheric pressure to a residual gas analyser operating at a vacuum of 10(-5)  mbar. The apparatus and methodology have been demonstrated to provide high sensitivity (ppb). The rate of degradation of NO2 attributed to reaction at the TiO2 surface was sensitive to both crystal structures (anatase or rutile) and wavelength of irradiation. PMID:25044899

  4. Beta zeolite supported sol-gel TiO2 materials for gas phase photocatalytic applications.

    PubMed

    Lafjah, Mama; Djafri, Fatiha; Bengueddach, Abdelkader; Keller, Nicolas; Keller, Valérie

    2011-02-28

    Beta zeolite supported sol-gel TiO(2) photocatalytic materials were prepared according to a sol-gel route in which high specific surface area Beta zeolite powder was incorporated into the titanium isopropoxide sol during the course of the sol-gel process. This led to an intimate contact between the zeolite surface and the TiO(2) precursors, and resulted in the anchorage of large amounts of dispersed TiO(2) nanoparticles and in the stabilization of TiO(2) in its anatase form, even for high TiO(2) wt. contents and high calcination temperatures. Taking the UV-A photocatalytic oxidation of methanol as gas phase target reaction, high methanol conversions were obtained on the Beta zeolite supported TiO(2) photocatalysts when compared to bulk sol-gel TiO(2), despite lower amounts of TiO(2) within the photoactive materials. The methanol conversion was optimum for about 40 wt.% TiO(2) loading and calcination temperatures of 500-600°C. PMID:21177024

  5. Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3.

    PubMed

    Hubbard, J S; Voecks, G E; Hobby, G L

    1975-08-01

    The major photoproduct obtained on irradiation of gaseous NH3 and CO mixtures is ammonium cyanate; lesser amounts of urea, biurea, biuret semi-carbazide, formamide and cyanide were observed. The formation of the major gas phase photolysis product may be rationalized by the following reaction sequence: (see article). Urea is probably formed from NH4NCO in a thermal reaction while formamide may result from the disproportionation of NH2CO. Photocatalytic syntheses of 14C-urea, -formamide, and -formadehyde are effected by irradiation of 14CO and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. These syntheses are catalyzed by ultraviolet wavelengths longer than those absorbed by the gaseous reactants. The syntheses are also effected when the surface material is first irradiated in the presence of CO followed by a dark incubation with NH3. Apparently, the initiating step is a light dependent formation of a reactive form of CO on the surface. A discussion is given on the possible contribution of these reactions to the abiotic synthesis of organic nitrogen compounds on Mars, on the primitive Earth and in interstellar space. PMID:1159801

  6. Spatial Separation of Charge Carriers in In2O3-x(OH)y Nanocrystal Superstructures for Enhanced Gas-Phase Photocatalytic Activity.

    PubMed

    He, Le; Wood, Thomas E; Wu, Bo; Dong, Yuchan; Hoch, Laura B; Reyes, Laura M; Wang, Di; Kübel, Christian; Qian, Chenxi; Jia, Jia; Liao, Kristine; O'Brien, Paul G; Sandhel, Amit; Loh, Joel Y Y; Szymanski, Paul; Kherani, Nazir P; Sum, Tze Chien; Mims, Charles A; Ozin, Geoffrey A

    2016-05-24

    The development of strategies for increasing the lifetime of photoexcited charge carriers in nanostructured metal oxide semiconductors is important for enhancing their photocatalytic activity. Intensive efforts have been made in tailoring the properties of the nanostructured photocatalysts through different ways, mainly including band-structure engineering, doping, catalyst-support interaction, and loading cocatalysts. In liquid-phase photocatalytic dye degradation and water splitting, it was recently found that nanocrystal superstructure based semiconductors exhibited improved spatial separation of photoexcited charge carriers and enhanced photocatalytic performance. Nevertheless, it remains unknown whether this strategy is applicable in gas-phase photocatalysis. Using porous indium oxide nanorods in catalyzing the reverse water-gas shift reaction as a model system, we demonstrate here that assembling semiconductor nanocrystals into superstructures can also promote gas-phase photocatalytic processes. Transient absorption studies prove that the improved activity is a result of prolonged photoexcited charge carrier lifetimes due to the charge transfer within the nanocrystal network comprising the nanorods. Our study reveals that the spatial charge separation within the nanocrystal networks could also benefit gas-phase photocatalysis and sheds light on the design principles of efficient nanocrystal superstructure based photocatalysts. PMID:27159793

  7. Gas-phase photocatalytic degradation of perchloroethylene on glass pellets immobilized with TiO{sub 2}

    SciTech Connect

    Hung, C.H.; Yuan, C.S.

    1998-12-31

    The objective of this research was to study gas-phase photocatalytic degradation of perchloroethylene (PCE) under illumination of four 10-W near-ultraviolet (UV) light lamps. Experiments were performed in a photocatalytic reactor packed with Degussa P-25 TiO{sub 2}-coated glass pellets. Anatase TiO{sub 2} was applied as the photocatalyst in the investigation. The effects of reaction parameters including influent PCE concentrations (10 to 50 ppm), water vapor content (0 to 100 % relative humidity), oxygen concentrations (0.31 to 21%), reactor space times (0.55 to 1.83 seconds), and irradiated light intensity (0.4 to 1.0 mW/cm{sup 2}) were investigated in the study. Experimental results indicated that fast photocatalytic degradation of PCE took place in the presence of TiO2 illuminated with near-UV light. Experimental results also showed that the highest degradation rate and quantum efficiency of PCE were 0.523 m mol/secgm and 5.2 %, respectively. The highest conversion ratio of PCE of 99.8 % was achieved in the study. Greater conversation ratios of PCE were observed for longer reaction time. Increase in the reaction rates of PCE by increasing influent PCE and oxygen concentrations were presented. Higher reaction rates of PCE under stronger illumination light intensity were detected. The degradation rates of PCE were proportional to light intensity with the power order of 1.2. On the other hand, the inhibited degradation of PCE was observed in the presence of water vapor. Lower reaction rates of PCE were detected when water vapor was present in the reaction. A modified Langmuir-Hishelwood kinetic was applied to model photocatalytic degradation of PCE. Two different adsorption sites on irradiated TiO2{sub 2} surfaces for the adsorption of PCE and oxygen molecules respectively were assumed in the model. The assumption of water vapor competing with PCE for reactive sites was considered in the reaction.

  8. Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3. [photolysis products

    NASA Technical Reports Server (NTRS)

    Hubbard, J. S.; Voecks, G. E.; Hobby, G. L.; Ferris, J. P.; Williams, E. A.; Nicodem, D. E.

    1975-01-01

    Ammonium cyanate is identified as the major product of the photolysis of gaseous NH3-CO mixtures at 206.2 or 184.9 nm. Lesser amounts of urea, biurea, biuret semicarbazide, formamide and cyanide are observed. A series of 18 reactions underlying the formation of photolysis products is presented and discussed. Photocatalytic syntheses of C-14-urea, -formamide, and -formaldehyde are carried out through irradiation of (C-14)O and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. The possible contributions of the relevant reactions to the abiotic synthesis of organic nitrogen compounds on Mars, the primitive earth, and in interstellar space are examined.

  9. Optimization of operating parameters for gas-phase photocatalytic splitting of H2S by novel vermiculate packed tubular reactor.

    PubMed

    Preethi, V; Kanmani, S

    2016-10-01

    Hydrogen production by gas-phase photocatalytic splitting of Hydrogen Sulphide (H2S) was investigated on four semiconductor photocatalysts including CuGa1.6Fe0.4O2, ZnFe2O3, (CdS + ZnS)/Fe2O3 and Ce/TiO2. The CdS and ZnS coated core shell particles (CdS + ZnS)/Fe2O3 shows the highest rate of hydrogen (H2) production under optimized conditions. Packed bed tubular reactor was used to study the performance of prepared photocatalysts. Selection of the best packing material is a key for maximum removal efficiency. Cheap, lightweight and easily adsorbing vermiculate materials were used as a novel packing material and were found to be effective in splitting H2S. Effect of various operating parameters like flow rate, sulphide concentration, catalyst dosage, light irradiation were tested and optimized for maximum H2 conversion of 92% from industrial waste H2S. PMID:27562700

  10. Parallelization of photocatalytic gas-producing reactions

    NASA Astrophysics Data System (ADS)

    Khnayzer, Rony S.; Martin, Douglas R.; Codding, Charles L.; Castellano, Felix N.

    2015-03-01

    High-throughput screening has been widely utilized in the pharmaceutical and manufacturing industry targeting the development of new molecules and materials for numerous applications. To enable more rapid progress in photocatalytic water-splitting reactions, the construction of high-throughput combinatorial photoreactors enabling the parallel optimization of relevant compositions under varieties of experimental conditions seems appropriate. This contribution describes a 16-photoreactor apparatus permitting the kinetic evaluation of photocatalytic gas-producing reactions using head-space pressure, gas chromatography, and mass spectrometry operating in parallel, illustrated with molecular-based homogeneous photocatalytic H2-generating compositions.

  11. Solving widespread low-concentration VOC air pollution problems: Gas-phase photocatalytic oxidation answers the needs of many small businesses

    SciTech Connect

    Lyons, C; Turchi, C; Gratson, D

    1995-04-01

    Many small businesses are facing new regulations under the 1990 Amendments to the Clean Air Act. Regulators, as well as the businesses themselves, face new challenges to control small point-source air pollution emissions. An individual business-such as a dry cleaner, auto repair shop, bakery, coffee roaster, photo print shop, or chemical company-may be an insignificant source of air pollution, but collectively, the industry becomes a noticeable source. Often the businesses are not equipped to respond to new regulatory requirements because of limited resources, experience, and expertise. Also, existing control strategies may be inappropriate for these businesses, having been developed for major industries with high volumes, high pollutant concentrations, and substantial corporate resources. Gas-phase photocatalytic oxidation (PCO) is an option for eliminating low-concentration, low-flow-rate emissions of volatile organic compounds (VOCs) from small business point sources. The advantages PCO has over other treatment techniques are presented in this paper. This paper also describes how PCO can be applied to specific air pollution problems. We present our methodology for identifying pollution problems for which PCO is applicable and for reaching the technology`s potential end users. PCO is compared to other gas-phase VOC control technologies.

  12. The effect of water presence on the photocatalytic oxidation of benzene, toluene, ethylbenzene and m-xylene in the gas-phase

    NASA Astrophysics Data System (ADS)

    Korologos, Christos A.; Philippopoulos, Constantine J.; Poulopoulos, Stavros G.

    2011-12-01

    In the present work, the gas-solid heterogeneous photocatalytic oxidation of benzene, toluene, ethylbenzene and m-xylene (BTEX) over UV-irradiated titanium dioxide was studied in an annular reactor operated in the CSTR (continuous stirred-tank reactor) mode. GC-FID and GC-MS were used for analysing reactor inlet and outlet streams. Initial BTEX concentrations were in the low parts per million (ppmv) range, whereas the water concentration was in the range of 0-35,230 ppmv and the residence time varied from 50 to 210 s. The effect of water addition on the photocatalytic process showed strong dependence on the type of the BTEX and the water vapour concentration. The increase in residence time resulted in a considerable increase in the conversion achieved for all compounds and experimental conditions. There was a clear interaction between residence time and water presence regarding the effect on conversions achieved. It was established that conversions over 95% could be achieved by adjusting appropriately the experimental conditions and especially the water concentration in the reactor. In all cases, no by-products were detected above the detection limit and carbon dioxide was the only compound detected. Finally, various Langmuir-Hinshelwood kinetic models have been tested in the analysis of the experimental data obtained. The kinetic data obtained confirmed that water had an active participation in the photocatalytic reactions of benzene, toluene, ethylbenzene and m-xylene since the model involving reaction of BTEX and water adsorbed on different active sites yielded the most successful fitting to the experimental results for the first three compounds, whereas the kinetic model based on the assumption that reaction between VOC and water dissociatively adsorbed on the photocatalyst takes place was the most appropriate in the case of m-xylene.

  13. Gas phase photocatalytic degradation on TiO{sub 2} pellets of volatile chlorinated organic compounds from a soil vapor extraction well

    SciTech Connect

    Yamazaki-Nishida, S.; Read, H.W.; Nagano, J.K.; Anderson, M.A.; Cervera-March, S.; Jarosch, T.R.; Eddy-Dilek, C.A.

    1993-05-20

    The mineralization of trichloroethylene (TCE) and tetrachloroethylene (PCE) in gas stream from a soil vapor extraction (SVE) well was demonstrated with an annular photocatalytic reactor packed with porous TiO{sub 2} pellets in field trials at the Savannah River Site in Aiken, SC. The TiO{sub 2} pellets were prepared using a sol-gel method. The experiments were performed at 55 to 60{degree}C using space times of 10{sup 8} to 10{sup 10} g s/mol for TCE and PCE. Chloroform (CHCl{sub 3}) and carbon tetrachloride (CCl{sub 4}) were detected as minor products from side reactions. On a molar basis, CCl{sub 4} and CHCl{sub 3} produced were about 2% and 0.2 % of the reactants.

  14. A new continuous device to perform S-L-G photocatalytic studies. [Solid-Liquid-Gas

    SciTech Connect

    Aguado, M.A.; Gimenez, J.; Simarro, R.; Cervera-March, S. )

    1992-07-01

    A new experimental device to carry out solid-liquid-gas photocatalytic studies is presented. It can operate as a continuous system with respect to both the gas and the liquid phase. The solid photocatalyst is held inside the system and is continuously recycled through it to enable the separation of the spent liquid. Steady values of liquid and gas composition as well as temperature and fluidodynamic variables can be set and controlled.

  15. Phase-dependent photocatalytic H2 evolution of copper zinc tin sulfide under visible light.

    PubMed

    Chang, Zhi-Xian; Zhou, Wen-Hui; Kou, Dong-Xing; Zhou, Zheng-Ji; Wu, Si-Xin

    2014-10-28

    CZTS exhibited apparently phase-dependent photocatalytic H2 evolution under visible light. Possible factors for the phase-dependent photocatalytic activity of CZTS were discussed in detail. PMID:25205452

  16. [Radiation transformation mechanism in a photocatalytic reactor of three-phase internal circulating fluidized bed].

    PubMed

    You, Hong; Luo, Wei-nan; Yao, Jie; Chen, Ping; Cai, Wei-min

    2005-01-01

    A novel three-phase internal circulating fluidized bed photocatalytic reactor was established and the radiation transformation in which was investigated. The experimental results indicate that with the interaction of gas and solid (gas flux > 0.3m3/h), the radiation transformation in the reactor along radial direction conforms to a definite exponential function, which agrees to formula Rose about the rules of light intensity distribution through evenly suspended particles. The value of radiation energy is affected by the initial light intensity, the concentration of photocatalyst and the thickness of liquid layer. The aerated gas amount only influence the state of the fluidized bed and has little effect on the distribution of light intensity along radical direction. Photocatalytic degradation of Rhodamine B indicate that the efficiency of three-phase internal circulating fluidized bed is much higher than slurry bed. The optimal catalyst concentration of this system is 10 - 12g/L. PMID:15859420

  17. Efficient photocatalytic degradation of organics present in gas and liquid phases using Pt-TiO2/Zeolite (H-ZSM).

    PubMed

    Neppolian, B; Mine, Shinya; Horiuchi, Yu; Bianchi, C L; Matsuoka, M; Dionysiou, D D; Anpo, M

    2016-06-01

    TiO2-encapsulated H-ZSM photocatalysts were prepared by physical mixing of TiO2 and zeolites. Pt was immobilized on the surface of the TiO2-encapsulated zeolite (H-ZSM) catalysts by a simple photochemical reduction method. Different weight ratios of both TiO2 and Pt were hybridized with H-ZSM and the catalytic performance of the prepared catalysts was investigated for 2-propanol oxidation in liquid phase and acetaldehyde in gas phase reaction. Around 5-10 wt% TiO2-encapsulated H-ZSM catalysts was found to be optimal amount for the effective oxidation of the organics. Prior to light irradiation, Pt-TiO2-H-ZSM showed considerable amount of catalytic degradation of 2-propanol in the dark, forming acetone as an intermediate. In this study, Pt has played a major and important role on the total oxidation of 2-propanol as well as acetaldehyde. As a result, no residual organics were present in the pores of the zeolites. The catalysts could be reused more than three times without losing their catalytic activity in both phases. The Pt-TiO2-H-ZSM photocatalysts could overcome the problem of strong adsorption of organics in the zeolite pores (after the reaction). Thus, Pt-TiO2-H-ZSM can be used as a potential catalyst for both liquid and gas phase oxidation of organic pollutants. PMID:27016820

  18. Solar photocatalytic gas-phase degradation of n-decane--a comparative study using cellulose acetate monoliths coated with P25 or sol-gel TiO₂ films.

    PubMed

    Miranda, Sandra M; Lopes, Filipe V S; Rodrigues-Silva, Caio; Martins, Susana D S; Silva, Adrián M T; Faria, Joaquim L; Boaventura, Rui A R; Vilar, Vítor J P

    2015-01-01

    Cellulose acetate monoliths (CAM) were used as the substrate for the deposition of TiO2 films to produce honeycombed photoactive structures to fill a tubular photoreactor equipped with a compound parabolic collector. By using such a setup, an efficient single-pass gas-phase conversion was achieved in the degradation of n-decane, a model volatile organic compound. The CAM three-dimensional, gas-permeable transparent structure with a rugged surface enables a good adhesion of the catalytic coating. It also provides a rigid structure for packing the tubular photoreactor, and maximizing the illuminated catalyst surface. The efficiency of the photocatalytic oxidation (PCO) process on n-decane degradation was evaluated under different operating conditions, such as feeding concentration (73 and 146 ppm), gas stream flow rate (73, 150, and 300 mL min(-1)), relative humidity (3 and 25 %), and UV irradiance (18.9, 29.1, and 38.4 WUV m(-2)). The results show that n-decane degradation by neat photolysis is negligible, but mineralization efficiencies of 86 and 82 % were achieved with P25-CAM and SG-CAM, respectively, for parent pollutant conversions above 95 %, under steady-state conditions. A mass transfer model, considering the mass balance to the plug-flow packed photoreactor, and PCO reaction given by a Langmuir-Hinshelwood bimolecular non-competitive two types of sites equation, was able to predict well the PCO kinetics under steady-state conditions, considering all the operational parameters tested. Overall, the performance of P25-CAM was superior taking into account mineralization efficiency, cost of preparation, surface roughness, and robustness of the deposited film. PMID:24809494

  19. Controllable synthesis of 3D BiVO₄ superstructures with visible-light-induced photocatalytic oxidation of NO in the gas phase and mechanistic analysis.

    PubMed

    Ou, Man; Nie, Haoyu; Zhong, Qin; Zhang, Shule; Zhong, Lei

    2015-11-21

    A surfactant-free solvothermal method was developed for the controlled synthesis of diverse 3D ms-BiVO4 superstructures, including a flower, a double-layer half-open flower and a hollow tube with square cross-sections, via facilely adjusting the pH values with the aid of NH3·H2O. The effects of the morphologies of the prepared 3D ms-BiVO4 superstructure on the photocatalytic oxidation of NO were investigated, indicating that the enhanced photoactivity was not related to the surface area, but associated with the unique morphology, surface structure and good crystallinity. Moreover, the flower-like ms-BiVO4 photocatalyst with a more (040) reactive crystal plane exhibited higher photoactivity than those of other samples. The unique morphology helped with flushing the oxidation products accumulated on the surface of photocatalysts in the H2O2 system, and further improved the photoactivity. A trapping experiment was also conducted to examine the effects of the active species involved in the PCO of NO intuitively. PMID:26451402

  20. Hematite nanoplates: Controllable synthesis, gas sensing, photocatalytic and magnetic properties.

    PubMed

    Hao, Hongying; Sun, Dandan; Xu, Yanyan; Liu, Ping; Zhang, Guoying; Sun, Yaqiu; Gao, Dongzhao

    2016-01-15

    Uniform hematite (α-Fe2O3) nanoplates exposing {001} plane as basal planes have been prepared by a facile solvothermal method under the assistance of sodium acetate. The morphological evolution of the nanoplates was studied by adjusting the reaction parameters including the solvent and the amount of sodium acetate. The results indicated that both the adequate nucleation/growth rate and selective adsorption of alcohol molecules and acetate anions contribute to the formation of the plate-like morphology. In addition, the size of the nanoplates can be adjusted from ca. 180nm to 740nm by changing the reaction parameters. Three nanoplate samples with different size were selected to investigate the gas sensing performance, photocatalytic and magnetic properties. As gas sensing materials, all the α-Fe2O3 nanoplates exhibited high gas sensitivity and stability toward n-butanol. When applied as photocatalyst, the α-Fe2O3 nanoplates show high photodegradation efficiency towards RhB. Both the gas sensing performance and the photocatalytic property of the products exhibit obvious size-dependent effect. Magnetic measurements reveal that the plate-like α-Fe2O3 particles possess good room temperature magnetic properties. PMID:26476200

  1. Valorization of Flue Gas by Combining Photocatalytic Gas Pretreatment with Microalgae Production.

    PubMed

    Eynde, Erik Van; Lenaerts, Britt; Tytgat, Tom; Blust, Ronny; Lenaerts, Silvia

    2016-03-01

    Utilization of flue gas for algae cultivation seems to be a promising route because flue gas from fossil-fuel combustion processes contains the high amounts of carbon (CO2) and nitrogen (NO) that are required for algae growth. NO is a poor nitrogen source for algae cultivation because of its low reactivity and solublilty in water and its toxicity for algae at high concentrations. Here, we present a novel strategy to valorize NO from flue gas as feedstock for algae production by combining a photocatalytic gas pretreatment unit with a microalgal photobioreactor. The photocatalytic air pretreatment transforms NO gas into NO2 gas and thereby enhances the absorption of NOx in the cultivation broth. The absorbed NOx will form NO2(-) and NO3(-) that can be used as a nitrogen source by algae. The effect of photocatalytic air pretreatment on the growth and biomass productivity of the algae Thalassiosira weissflogii in a semicontinuous system aerated with a model flue gas (1% CO2 and 50 ppm of NO) is investigated during a long-term experiment. The integrated system makes it possible to produce algae with NO from flue gas as the sole nitrogen source and reduces the NOx content in the exhaust gas by 84%. PMID:26838336

  2. Gas Phase Nanoparticle Synthesis

    NASA Astrophysics Data System (ADS)

    Granqvist, Claes; Kish, Laszlo; Marlow, William

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

  3. Hydrothermal synthesis, phase structure, optical and photocatalytic properties of Zn2SnO4 nanoparticles.

    PubMed

    Ben Ali, Monaam; Barka-Bouaifel, Fatiha; Elhouichet, Habib; Sieber, Brigitte; Addad, Ahmed; Boussekey, Luc; Férid, Mokhtar; Boukherroub, Rabah

    2015-11-01

    Zinc stannate (Zn2SnO4 or ZTO) nanoparticles were synthesized via hydrothermal method using NaOH as a mineralizer. X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) of the synthesized ZTO nanoparticles revealed the formation of highly pure ZTO phase with the spinel-like structure. The nanoparticles have spherical shape with an average size of about 25 nm. The Raman spectrum of the sample was dominated by the A(1g) vibration mode of pure ZTO phase. From UV-Vis measurement, a band gap E(g) of 3.465 eV was determined. The photocatalytic activity of the ZTO nanoparticles was evaluated for the photodegradation of rhodamine B (RhB) under visible light irradiation. The influence of catalyst concentration and irradiation time on the photocatalytic process was investigated. The ZTO catalyst showed the best photocatalytic performance at a concentration of 0.2 g/L, and the photodecomposition of RhB followed first-order kinetics with a rate constant k=0.0249 min(-1). The ZTO-assisted photocatalytic degradation of RhB occurred via two competitive processes: a photocatalytic process and a photosensitized process. The detection of hydroxyl radicals by fluorescence measurements suggests that these species play an important role in the photocatalytic process. PMID:26196720

  4. Phase dependent photocatalytic activity of Ag loaded TiO2 films under sun light

    NASA Astrophysics Data System (ADS)

    Madhavi, V.; Kondaiah, P.; Shaik, Habibuddin; Rao, G. Mohan

    2016-02-01

    Well-crystallized anatase and mixed (anatase-rutile) phase TiO2 thin films were deposited by DC magnetron sputtering technique at various DC powers in the range of 80-140 W. Pure anatase phase was observed in the TiO2 films deposited at low power of 80 W. Films deposited at 120 W were composed of both anatase and rutile phases. At higher power of 140 W, the films are rutile dominated and the rutile percentage increased from 0 to 82% with increase of DC power. The same results of phase change were confirmed by Raman studies. The surface morphology of the TiO2 films showed that the density of the films increased with increase of sputter power. The optical band gap of the films varied from 3.35 to 3.14 eV with increase of DC power. The photocatalytic activity of the TiO2 films increased with increasing DC power up to 120 W and after that it decreases. We found that the TiO2 films deposited at 120 W with 48% of rutile phase, exhibited high photocatalytic activity (43% of degradation) under UV light compared with other TiO2 films. After loading the optimized Ag nanoparticles on the mixed phase TiO2 films, the photocatalytic activity shifted from UV to visible region with enhancement of photocatalytic activity (55% of degradation).

  5. High photocatalytic activity of mixed anatase-rutile phases on commercial TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Ruu Siah, Wai; Lintang, Hendrik O.; Shamsuddin, Mustaffa; Yuliati, Leny

    2016-02-01

    Titanium dioxide (TiO2) is well-known as an active photocatalyst for degradation of various organic pollutants. Over the years, a wide range of TiO2 nanoparticles with different phase compositions, crystallinities, and surface areas have been developed. Due to the different methods and conditions used to synthesize these commercial TiO2 nanoparticles, the properties and photocatalytic performance would also be different from each other. In this study, the photocatalytic removal of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5- trichlorophenoxyacetic acid (2,4,5-T) was investigated on commercial Evonik P25, Evonik P90, Hombikat UV100 and Hombikat N100 TiO2 nanoparticles. Upon photocatalytic tests, it was found that overall, the photocatalytic activities of the P25 and the P90 were higher than the N100 and the UV100 for the removal of both 2,4-D and 2,4,5-T. The high activities of the P25 and the P90 could be attributed to their phase compositions, which are made up of a mixture of anatase and rutile phases of TiO2. Whereas, the UV100 and the N100 are made up of 100% anatase phase of TiO2. The synergistic effect of the anatase/rutile mixture was reported to slow down the recombination rate of photogenerated electron-hole pairs. Consequently, the photocatalytic activity was increased on these TiO2 nanoparticles.

  6. Photocatalytic oxidation of methyl orange in water phase by immobilized TiO2-carbon nanotube nanocomposite photocatalyst

    NASA Astrophysics Data System (ADS)

    Dong, Yinmao; Tang, Dongyan; Li, Chensha

    2014-03-01

    We developed an immobilized carbon nanotube (CNT)-titanium dioxide (TiO2) heterostructure material for the photocatalytic oxidation of methyl orange in aqueous phase. The catalyst material was prepared via sol-gel method using multi-walled CNTs grown on graphite substrate as carriers. The multi-walled CNTs were synthesized from thermal decomposing of hydrocarbon gas directly on thin graphite plate, forming immobilized 3-dimensional network of CNTs. The nanophase TiO2 was synthesized coating on CNTs to form "coral"-shaped nanocomposite 3-dimensional network on graphite substrate, thus bringing effective porous structure and high specific surface area, and possessing the merit of dispersive powder photocatalysts, which is the fully available surface area, while adapting the requirement for clean and convenient manipulation as an immobilized photocatalyst. Moreover, the CNT-TiO2 heterostructure reduced the electron-hole pair recombination rate and enhanced the photoabsorption and the adsorption ability, resulting in elevating the photocatalysis efficiency. These synergistic effects due to the hybrid nature of the materials and interphase interaction greatly improved the catalytic activity, and demonstrated superior photocatalytic performances. Our work can be a significant inspiration for developing hybrid nano-phase materials to realize sophisticated functions, and bear tremendous significance for the development and applications of semiconductor nano-materials.

  7. Gas-phase chemical dynamics

    SciTech Connect

    Weston, R.E. Jr.; Sears, T.J.; Preses, J.M.

    1993-12-01

    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.

  8. Low temperature fabrication & photocatalytical activity of carbon fiber-supported TiO2 with different phase compositions.

    PubMed

    Wang, Zhifeng; Yoshinaga, Kohji; Bu, Xiu R; Zhang, Ming

    2015-06-15

    Crystalline TiO2 nanoparticles with different phase compositions were fabricated on carbon fibers. The fabrication is achieved at low temperature. The process includes the treatment of Ti(OH)4 with hydrogen peroxide in the presence of carbon fibers. Neither additional acids nor bases, or additives are used during the process. Carbon fibers prior to and after TiO2 loading are characterized by FE-SEM, XRD, and UV-vis absorption spectroscopy. The photocatalytic activity was assessed via photocatalytic degradation of methyl orange solution, and found to be phase composition-dependent & pH dependent. Carbon fibers loaded with mixed-phase TiO2 led to the best photocatalytic performance. HRTEM reveals the anatase/rutile heterojunction which helps explain the high efficiency of photocatalysis. They have been demonstrated to be re-usable in the continuous photocatalytic degradation process. PMID:25791498

  9. Efficient Photocatalytic Activities of TiO2 Hollow Fibers with Mixed Phases and Mesoporous Walls

    PubMed Central

    Hou, Huilin; Shang, Minghui; Wang, Lin; Li, Wenge; Tang, Bin; Yang, Weiyou

    2015-01-01

    Currently, Degussa P25, with the typical mixed phases of anatase and rutile TiO2, is widely applied as the commercial photocatalysts. However, there are still some of obstacles for the P25 nanoparticles with totally high photocatalytic activities, especially for the catalytic stability due to their inevitable aggregation of the nanoparticles when used as the photocatalysts. In the present work, we reported the exploration of a novel TiO2 photocatalyst, which could offer an ideal platform for synergetic combination of the mixed-phase composition, hollow architecture and mesoporous walls for the desired excellent photocatalytic efficiency and robust stability. The mesoporous TiO2 hollow nanofibers were fabricated via a facile single capillary electrospinning technique, in which the foaming agents were used for creating mesopores throughout the walls of the hollow fibers. The obtained hollow fibers exhibit a high purity and possess the mixed phases of 94.6% anatase and 5.4% rutile TiO2. As compared to P25, the as-fabricated mesoporous TiO2 hollow fibers exhibited much higher efficient photocatalytic activities and stabilities toward the hydrogen evolution with a rate of ~499.1 μmol g−1·h−1 and ~99.5% degradation Rhodamine B (RhB) in 60 min, suggesting their promising application in efficient photocatalysts. PMID:26470013

  10. Efficient Photocatalytic Activities of TiO2 Hollow Fibers with Mixed Phases and Mesoporous Walls.

    PubMed

    Hou, Huilin; Shang, Minghui; Wang, Lin; Li, Wenge; Tang, Bin; Yang, Weiyou

    2015-01-01

    Currently, Degussa P25, with the typical mixed phases of anatase and rutile TiO2, is widely applied as the commercial photocatalysts. However, there are still some of obstacles for the P25 nanoparticles with totally high photocatalytic activities, especially for the catalytic stability due to their inevitable aggregation of the nanoparticles when used as the photocatalysts. In the present work, we reported the exploration of a novel TiO2 photocatalyst, which could offer an ideal platform for synergetic combination of the mixed-phase composition, hollow architecture and mesoporous walls for the desired excellent photocatalytic efficiency and robust stability. The mesoporous TiO2 hollow nanofibers were fabricated via a facile single capillary electrospinning technique, in which the foaming agents were used for creating mesopores throughout the walls of the hollow fibers. The obtained hollow fibers exhibit a high purity and possess the mixed phases of 94.6% anatase and 5.4% rutile TiO2. As compared to P25, the as-fabricated mesoporous TiO2 hollow fibers exhibited much higher efficient photocatalytic activities and stabilities toward the hydrogen evolution with a rate of ~499.1 μmol g(-1)·h(-1) and ~99.5% degradation Rhodamine B (RhB) in 60 min, suggesting their promising application in efficient photocatalysts. PMID:26470013

  11. Efficient Photocatalytic Activities of TiO2 Hollow Fibers with Mixed Phases and Mesoporous Walls

    NASA Astrophysics Data System (ADS)

    Hou, Huilin; Shang, Minghui; Wang, Lin; Li, Wenge; Tang, Bin; Yang, Weiyou

    2015-10-01

    Currently, Degussa P25, with the typical mixed phases of anatase and rutile TiO2, is widely applied as the commercial photocatalysts. However, there are still some of obstacles for the P25 nanoparticles with totally high photocatalytic activities, especially for the catalytic stability due to their inevitable aggregation of the nanoparticles when used as the photocatalysts. In the present work, we reported the exploration of a novel TiO2 photocatalyst, which could offer an ideal platform for synergetic combination of the mixed-phase composition, hollow architecture and mesoporous walls for the desired excellent photocatalytic efficiency and robust stability. The mesoporous TiO2 hollow nanofibers were fabricated via a facile single capillary electrospinning technique, in which the foaming agents were used for creating mesopores throughout the walls of the hollow fibers. The obtained hollow fibers exhibit a high purity and possess the mixed phases of 94.6% anatase and 5.4% rutile TiO2. As compared to P25, the as-fabricated mesoporous TiO2 hollow fibers exhibited much higher efficient photocatalytic activities and stabilities toward the hydrogen evolution with a rate of ~499.1 μmol g-1·h-1 and ~99.5% degradation Rhodamine B (RhB) in 60 min, suggesting their promising application in efficient photocatalysts.

  12. Photocatalytic Activity of Nanostructured Anatase Coatings Obtained by Cold Gas Spray

    NASA Astrophysics Data System (ADS)

    Gardon, M.; Fernández-Rodríguez, C.; Garzón Sousa, D.; Doña-Rodríguez, J. M.; Dosta, S.; Cano, I. G.; Guilemany, J. M.

    2014-10-01

    This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS) supported on titanium sub-oxide (TiO2- x ) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO2 particles fragmented when impacting onto the hard surface of the APS TiO2- x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO2 coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25® photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.

  13. Enhanced Photocatalytic Activity of Bismuth Precursor by Rapid Phase and Surface Transformation Using Structure-Guided Combustion Waves.

    PubMed

    Lee, Kang Yeol; Hwang, Hayoung; Kim, Tae Ho; Choi, Wonjoon

    2016-02-10

    The development of an efficient method for manipulating phase and surface transformations would facilitate the improvement of catalytic materials for use in a diverse range of applications. Herein, we present the first instance of a submicrosecond time frame direct phase and surface transformation of Bi(NO3)3 rods to nanoporous β-Bi2O3 rods via structure-guided combustion waves. Hybrid composites of the prepared Bi(NO3)3·H2O rods and organic fuel were fabricated by a facile preparation method. The anisotropic propagation of combustion waves along the interfacial boundaries of Bi(NO3)3·H2O rods induced direct phase transformation to β-Bi2O3 rods in the original structure due to the rapid pyrolysis, while the release of gas molecules enabled the formation of nanoporous structures on the surfaces of rods. The developed β-Bi2O3 rods showed improved photocatalytic activity for the photodegradation of rhodamine B in comparison with Bi(NO3)3·H2O rods and α-Bi2O3 rods due to the more suitable interdistance and the large contact areas of the porous surfaces. This new method of using structure-guided combustion waves for phase and surface transformation may contribute to the development of new catalysts as well as the precise manipulation of diverse micronanostructured materials. PMID:26765959

  14. Pressure-induced phase transitions of exposed curved surface nano-TiO2 with high photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Huang, Yanwei; Chen, Fengjiao; Li, Xin; Yuan, Ye; Dong, Haini; Samanta, Sudeshna; Yu, Zhenhai; Rahman, Saqib; Zhang, Jun; Yang, Ke; Yan, Shuai; Wang, Lin

    2016-06-01

    We report a unique phase transition in compressed exposed curved surface nano-TiO2 with high photocatalytic activity using in situ synchrotron X-ray diffraction and Raman Spectroscopy. High-pressure studies indicate that the anatase phase starts to transform into baddeleyite phase upon compression at 19.4 GPa, and completely transforms into the baddeleyite phase above 24.6 GPa. Upon decompression, the baddeleyite phase was maintained until the pressure was released to 6.4 GPa and then transformed into the α-PbO2 phase at 2.7 GPa. Together with the results of high-resolution transmission electron microscopy and the pressure-volume relationship, this phase transition's characteristics during the compression-decompression cycle demonstrate that the truncated biconic morphology possessed excellent stability. This study may provide an insight to the mechanisms of stability for high photocatalytic activity of nano-TiO2.

  15. Photocatalytic abatement of NOx by C-TiO2/polymer composite coatings obtained by low pressure cold gas spraying

    NASA Astrophysics Data System (ADS)

    Robotti, M.; Dosta, S.; Fernández-Rodríguez, C.; Hernández-Rodríguez, M. J.; Cano, I. G.; Melián, E. Pulido; Guilemany, J. M.

    2016-01-01

    In the present work, we study the photocatalytic activity of carbon-modified TiO2 (C-TiO2)/polymer composite coatings obtained by low pressure cold gas spraying (LP-CGS). To produce the novel coatings, C-TiO2 was mixed with a ductile material, the polymer ECTFE, by means of a low energy ball milling (LEBM) process. The LEBM system permits the mechanical anchoring of small TiO2 aggregates around the large ductile polymeric particles. A well-bonded coating with good mechanical coupling was formed between the ball-milled mixture and the substrate. Photocatalytic tests showed that the LP-CGS nano-TiO2 coatings actively photodegraded NO and the by-product, NO2. Compared to commercial paint, the as-prepared coatings presented here enhanced photocatalytic performance.

  16. High rate deposition of photocatalytic TiO{sub 2} films with high activity by hollow cathode gas-flow sputtering method

    SciTech Connect

    Kubo, Yoshiyuki; Iwabuchi, Yoshinori; Yoshikawa, Masato; Sato, Yasushi; Shigesato, Yuzo

    2008-07-15

    Photocatalytic TiO{sub 2} films were deposited by a hollow cathode gas-flow sputtering method using two Ti metal targets mounted parallel to each other. The Ar and O{sub 2} flow rates were 3000 and 0-50 SCCM (SCCM denotes cubic centimeter per minute at STP), respectively, and total gas pressure during the deposition was maintained at 45 Pa. The highest deposition rate for the photocatalytic TiO{sub 2} films was 162 nm/min at 30 SCCM of O{sub 2} flow. The as-deposited films and postannealed films, annealed in air at 300 deg. C for 1 h, were used to carry out photocatalytic decomposition of acetaldehyde (CH{sub 3}CHO). In particular, the postannealed films showed extremely high photocatalytic activity compared to the photocatalytic activity of films deposited by conventional reactive sputtering.

  17. Solid-phase photocatalytic degradation of polyethylene film with manganese oxide OMS-2

    NASA Astrophysics Data System (ADS)

    Liu, Guanglong; Liao, Shuijiao; Zhu, Duanwei; Cui, Jingzhen; Zhou, Wenbing

    2011-01-01

    Solid-phase photocatalytic degradation of polyethylene (PE) film with cryptomelane-type manganese oxide (OMS-2) as photocatalyst was investigated in the ambient air under ultraviolet and visible light irradiation. The properties of the composite films were compared with those of the pure PE film through performing weight loss monitoring, IR spectroscopy, scanning electron microscopic (SEM) and X-ray photoelectron spectroscopy (XPS). The photoinduced degradation of PE-OMS-2 composite films was higher than that of the pure films, while there has been little change under the visible light irradiation. The weight loss of PE-OMS-2 (1.0 wt%) composite films steadily decreased and reached 16.5% in 288 h under UV light irradiation. Through SEM observation there were some cavities on the surface of composite films, but few change except some surface chalking phenomenon occurred in pure PE film. The degradation rate with ultraviolet irradiation is controllable by adjusting the content of OMS-2 particles in PE plastic. Finally, the mechanism of photocatalytic degradation of the composite films was briefly discussed.

  18. Phase-controllable synthesis of nanosized nickel phosphides and comparison of photocatalytic degradation ability

    NASA Astrophysics Data System (ADS)

    Ni, Yonghong; Jin, Lina; Hong, Jianming

    2011-01-01

    In this paper, we employed a facile hydrothermal route to successfully synthesize nanosized nickel phosphide particles with controlled phases via selecting different surfactants at different temperatures and times. The phases of the as-obtained products were determined by X-ray powder diffraction (XRD) patterns and Rietveld refinement of XRD data. The morphologies of the products were characterized by (high resolution) transmission electron microscopy (HR/TEM) and field emission scanning electron microscopy (FESEM). Experiments indicated that pure Ni2P phase could be prepared when nontoxic red phosphorus and nickel dichloride were used as starting materials in the presence of polyvinylpyrrolidone (PVP, 30 K), sodium dodecylbenzene sulfonate (SDBS), cetyltrimethylammonium bromide (CTAB) or polyethylene glycol 10000 (PEG-10000) at 160 °C for 10 h. When acrylamide (AM) was selected as the surfactant, however, pure Ni12P5 phase could be prepared by prolonging the reaction time to 20 h at 160 °C, or enhancing the reaction temperature to 180 °C for 10 h. Furthermore, the experiments indicated that the pure Ni2P phase possessed a stronger photocatalytic degradation ability than the pure Ni12P5 phase.

  19. Phase-controllable synthesis of nanosized nickel phosphides and comparison of photocatalytic degradation ability.

    PubMed

    Ni, Yonghong; Jin, Lina; Hong, Jianming

    2011-01-01

    In this paper, we employed a facile hydrothermal route to successfully synthesize nanosized nickel phosphide particles with controlled phases via selecting different surfactants at different temperatures and times. The phases of the as-obtained products were determined by X-ray powder diffraction (XRD) patterns and Rietveld refinement of XRD data. The morphologies of the products were characterized by (high resolution) transmission electron microscopy (HR/TEM) and field emission scanning electron microscopy (FESEM). Experiments indicated that pure Ni2P phase could be prepared when nontoxic red phosphorus and nickel dichloride were used as starting materials in the presence of polyvinylpyrrolidone (PVP, 30 K), sodium dodecylbenzene sulfonate (SDBS), cetyltrimethylammonium bromide (CTAB) or polyethylene glycol 10000 (PEG-10000) at 160 °C for 10 h. When acrylamide (AM) was selected as the surfactant, however, pure Ni12P5 phase could be prepared by prolonging the reaction time to 20 h at 160 °C, or enhancing the reaction temperature to 180 °C for 10 h. Furthermore, the experiments indicated that the pure Ni2P phase possessed a stronger photocatalytic degradation ability than the pure Ni12P5 phase. PMID:21049133

  20. High visible light photocatalytic property of Co2+-doped TiO2 nanoparticles with mixed phases

    NASA Astrophysics Data System (ADS)

    Zhao, Cong; Shu, Xin; Zhu, Da-chuan; Wei, Shang-hai; Wang, Yu-xin; Tu, Ming-jing; Gao, Wei

    2015-12-01

    Mixed phases Co2+-doped TiO2 nanoparticles have been prepared by a novel method combined with sol-gel and hydrothermal methods. The section of sol-gel method, sol, provides an unstable colloidal reaction system for the next reaction process. The hydrothermal method is to treat the above reaction system to prepare undoped and doped samples. The as-prepared samples have been characterized by XRD, SEM, TEM, HRTEM and UV-vis spectroscopy. The results show that the as-prepared samples contain three titania polymorphs: brookite, rutile and anatase phases. These titania polymorphs probably form polymorph-junctions that can extend the lifetime of photogenerated electron-hole pairs. The photocatalytic activity has been evaluated by the photocatalytic degradation of Rhodamine B in air under visible-light irradiation. The degradation results indicate that the photocatalytic activity of as-prepared samples is higher than that of Degussa P25, especially the doped sample. This is ascribed to the fact that the phases with smaller band gap can enhance visible-light photocatalytic activity, the polymorph-junctions effectively extend the photoelectron lifetime and the nano size effect and Co-doping induce the shift of the absorption edge into the visible-light region. Furthermore, the XRD, SEM, and TEM data indicate that Co2+-doping results in the decrease of particle size.

  1. Facile synthesis and photocatalytic activity of bi-phase dispersible Cu-ZnO hybrid nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Xiao; Liu, HongLing; Zhang, WenXing; Li, XueMei; Fang, Ning; Wang, XianHong; Wu, JunHua

    2015-04-01

    Bi-phase dispersible Cu-ZnO hybrid nanoparticles were synthesized by one-pot non-aqueous nanoemulsion with the use of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) show high crystallinity of the Cu-ZnO hybrid nanoparticles and an average particle size of ~19.4 nm. The ultraviolet-visible light absorbance spectrometry (UV-vis) and photoluminescence spectrophotometry (PL) demonstrate well dispersibility and excellent optical performance of Cu-ZnO hybrid nanoparticles both in organic and aqueous solvent. The X-ray photoelectron spectroscopy (XPS) confirms Cu1+ and Cu2+ in ZnO. The observation using Sudan red (III) as probe molecule reveals that the Cu-ZnO hybrid nanoparticles possess enhanced photocatalytic activity and stability which are promising for potential applications in photocatalysis.

  2. Rate processes in gas phase

    NASA Technical Reports Server (NTRS)

    Hansen, C. F.

    1983-01-01

    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 for reaction. The effect of cross section function shape and of excited state contributions to 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. Influence of crystalline phase and defects in the ZrO{sub 2} nanoparticles synthesized by thermal plasma route on its photocatalytic properties

    SciTech Connect

    Nawale, Ashok B.; Kanhe, Nilesh S.; Bhoraskar, S.V.; Mathe, V.L.; Das, A.K.

    2012-11-15

    Graphical abstract: Thermal plasma synthesized nanophase zirconia showing the blue shift in the band gap of monoclinic phase as found from the photoabsorption spectroscopy was found to be the dominant parameter for the enhancement in its photocatalytic activity. The existence of different defect states and their concentration in as synthesized samples also inferred from the photoabsorption measurements were also found to be responsible for the enhanced photocatalytic activity of the samples. Highlights: ► Phase controlled structural formation of nanophase ZrO{sub 2} by thermal plasma route. ► Enhanced photocatalytic degradation rate of methylene blue dye. ► The blue shift in the band gap of monoclinic phase of nanocrystalline ZrO{sub 2}. ► Existence of different defect states in the as synthesized nano phase ZrO{sub 2}. ► Several competing processes which controls the photocatalytic degradation rate. -- Abstract: The photocatalytic activity of pure ZrO{sub 2} samples, prepared by a thermal plasma route, and characterized by X-ray diffraction technique was tested for the degradation of methylene blue, which is known to be a hazardous dye. Although, all these samples synthesized at different operating pressures of the thermal plasma reactor showed the photocatalytic activity; the sample synthesized at 1.33 bar of operating pressure showed the highest photocatalytic activity. The blue shift in the band gap of monoclinic phase, as observed from the photo-absorption spectroscopy, may be attributed to the enhanced photocatalytic activity. The existence of different defect states and their concentration as, inferred from the photo-absorption measurements were also found to be responsible for the enhanced photocatalytic activity of the as synthesized samples.

  4. Nonaqueous seeded growth of flower-like mixed-phase titania nanostructures for photocatalytic applications

    SciTech Connect

    Hsu, Y.-C.; Lin, H.-C.; Chen, C.-H.; Liao, Y.-T.; Yang, C.-M.

    2010-09-15

    A nonaqueous seeded-grown synthesis of three-dimensional TiO{sub 2} nanostructures in the benzyl alcohol reaction system was reported. The synthesis was simple, high-yield, and requires no structural directing or capping agents. It could be largely accelerated by applying microwave heating. The TiO{sub 2} nanostructures had a unique flower-like morphology and high surface area. Furthermore, the structural analyses suggested that the nanostructures had a non-uniform distribution of crystalline phases, with the inner part rich in anatase and the outer part rich in rutile. After heat treatments, the mixed-phase TiO{sub 2} nanostructures exhibited high photocatalytic activities for the photodegradation of methylene blue as compared to Degussa P25. The high photoactivities may be associated with the high surface area and the synergistic effect resulting from the anisotropic mixed-phase nanostructures. The results demonstrate the uniqueness of the nonaqueous seeded growth and the potential of the TiO{sub 2} nanostructures for practical applications. - Graphical abstract: Flower-like TiO{sub 2} nanostructures synthesized by a nonaqueous seeded growth without using any structural directing or capping agents.

  5. Mesoporous mixed-phase Ga{sub 2}O{sub 3}: Green synthesis and enhanced photocatalytic activity

    SciTech Connect

    Liu, Jin; Zhang, Gaoke

    2015-08-15

    Highlights: • Mixed-phase Ga{sub 2}O{sub 3} was synthesized by a facile and green method. • Mixed-phase Ga{sub 2}O{sub 3} exhibited good photocatalytic activity and stability. • The reactive species in the photocatalytic process were investigated. - Abstract: Mesoporous mixed-phase Ga{sub 2}O{sub 3} was synthesized by calcining the GaOOH precursor. The composition, crystal phase and microstructures of Ga{sub 2}O{sub 3} were characterized in detail. The phase composition of the as-prepared Ga{sub 2}O{sub 3} depended on the calcination temperature and the mixed-phase Ga{sub 2}O{sub 3} was obtained at 600–700 °C. As compared to the pure-phase α-Ga{sub 2}O{sub 3} and β-Ga{sub 2}O{sub 3}, the mixed-phase Ga{sub 2}O{sub 3} exhibited an enhanced photocatalytic property for the degradation of metronidazole solution. The heterojunction in the mixed-phase Ga{sub 2}O{sub 3} was beneficial to the separation of photogenerated electrons and holes. Moreover, the mixed-phase Ga{sub 2}O{sub 3} possessed mesopore structure, which increased more reaction sites and was in favor of the contact of metronidazole molecules with reaction sites. The recycling experiments show that the mixed-phase Ga{sub 2}O{sub 3} has good stability and can be separated easily from the reaction system.

  6. One-pot solvothermal synthesis of dual-phase titanate/titania Nanoparticles and their adsorption and photocatalytic Performances

    SciTech Connect

    Cheng, Yu Hua; Gong, Dangguo; Tang, Yuxin; Ho, Jeffery Weng Chye; Tay, Yee Yan; Lau, Wei Siew; Wijaya, Olivia; Lim, Jiexiang; Chen, Zhong

    2014-06-01

    Dual phase titanate/titania nanoparticles undergo phase transformation gradually with the increase of solvothermal synthesis temperature from 100 °C to 200 °C, and eventually are fully transformed into anatase TiO{sub 2}. The crystal structure change results in the changes of optical absorption, sensitizer/dopant formation and surface area of the materials which finally affect the overall dye removal ability. Reactions under dark and light have been conducted to distinguish the contributions of surface adsorption from photocatalytic degradation. The sample synthesized at 160 °C (S160) shows the best performances for both adsorption under dark and photocatalytic degradation of methylene blue (MB) under visible light irradiation. The adsorption mechanism for S160 is determined as monolayer adsorption based on the adsorption isotherm test under dark condition, and an impressive adsorption capacity of 162.19 mg/g is achieved. For the photocatalytic application, this sample at 0.1 g/L loading is also able to degrade 20 ppm MB within 6 hours under the visible light (>420 nm) condition. - Graphical abstract: The effect of solvothermal synthesis temperature on the formation and dye removal performance of dual phase titanate/titania nanoparticles was unveiled and optimized. - Highlights: • Low temperature one-pot solvothermal synthesis of dual-phase photocatalysts. • Correlation of the synthesis temperature is made with the phase composition. • Adsorption isotherm, kinetics, photocatalytic degradation were studied. • Synthesis at 160 °C yields the best material for adsorption of MB in dark. • The same sample also shows the best visible light degradation of MB.

  7. Photocatalytical Antibacterial Activity of Mixed-Phase TiO2 Nanocomposite Thin Films against Aggregatibacter actinomycetemcomitans.

    PubMed

    Yeniyol, Sinem; Mutlu, Ilven; He, Zhiming; Yüksel, Behiye; Boylan, Robert Joseph; Ürgen, Mustafa; Karabuda, Zihni Cüneyt; Basegmez, Cansu; Ricci, John Lawrence

    2015-01-01

    Mixed-phase TiO2 nanocomposite thin films consisting of anatase and rutile prepared on commercially pure Ti sheets via the electrochemical anodization and annealing treatments were investigated in terms of their photocatalytic activity for antibacterial use around dental implants. The resulting films were characterized by scanning electron microscopy (SEM), and X-ray diffraction (XRD). The topology was assessed by White Light Optical Profiling (WLOP) in the Vertical Scanning Interferometer (VSI) mode. Representative height descriptive parameters of roughness R a and R z were calculated. The photocatalytic activity of the resulting TiO2 films was evaluated by the photodegradation of Rhodamine B (RhB) dye solution. The antibacterial ability of the photocatalyst was examined by Aggregatibacter actinomycetemcomitans suspensions in a colony-forming assay. XRD showed that anatase/rutile mixed-phase TiO2 thin films were predominantly in anatase and rutile that were 54.6 wt% and 41.9 wt%, respectively. Craters (2-5 µm) and protruding hills (10-50 µm) on Ti substrates were produced after electrochemical anodization with higher R a and R z surface roughness values. Anatase/rutile mixed-phase TiO2 thin films showed 26% photocatalytic decolorization toward RhB dye solution. The number of colonizing bacteria on anatase/rutile mixed-phase TiO2 thin films was decreased significantly in vitro. The photocatalyst was effective against A. actinomycetemcomitans colonization. PMID:26576430

  8. Photocatalytical Antibacterial Activity of Mixed-Phase TiO2 Nanocomposite Thin Films against Aggregatibacter actinomycetemcomitans

    PubMed Central

    Yeniyol, Sinem; Mutlu, Ilven; He, Zhiming; Yüksel, Behiye; Boylan, Robert Joseph; Ürgen, Mustafa; Karabuda, Zihni Cüneyt; Basegmez, Cansu; Ricci, John Lawrence

    2015-01-01

    Mixed-phase TiO2 nanocomposite thin films consisting of anatase and rutile prepared on commercially pure Ti sheets via the electrochemical anodization and annealing treatments were investigated in terms of their photocatalytic activity for antibacterial use around dental implants. The resulting films were characterized by scanning electron microscopy (SEM), and X-ray diffraction (XRD). The topology was assessed by White Light Optical Profiling (WLOP) in the Vertical Scanning Interferometer (VSI) mode. Representative height descriptive parameters of roughness Ra and Rz were calculated. The photocatalytic activity of the resulting TiO2 films was evaluated by the photodegradation of Rhodamine B (RhB) dye solution. The antibacterial ability of the photocatalyst was examined by  Aggregatibacter actinomycetemcomitans suspensions in a colony-forming assay. XRD showed that anatase/rutile mixed-phase TiO2 thin films were predominantly in anatase and rutile that were 54.6 wt% and 41.9 wt%, respectively. Craters (2–5 µm) and protruding hills (10–50 µm) on Ti substrates were produced after electrochemical anodization with higher Ra and Rz surface roughness values. Anatase/rutile mixed-phase TiO2 thin films showed 26% photocatalytic decolorization toward RhB dye solution. The number of colonizing bacteria on anatase/rutile mixed-phase TiO2 thin films was decreased significantly in vitro. The photocatalyst was effective against A. actinomycetemcomitans colonization. PMID:26576430

  9. Photocatalytic Properties of TiO2 Thin Films Modified with Ag and Pt Nanoparticles Deposited by Gas Flow Sputtering.

    PubMed

    Maicu, M; Glöss, D; Frach, Peter; Hecker, D; Gerlach, G; Córdoba, José M

    2015-09-01

    In this work, a gas flow sputtering (GFS) process which allows the production and deposition of metal nanoparticles (NPs) in a vacuum environment is described. Aim of the study is to prove the potential of this technology for the fabrication of new TiO2 films with enhanced photocatalytic properties. For this purpose, Ag and Pt NPs have been produced and deposited on photocatalytic float glass coated with TiO2 thin films by magnetron sputtering. The influence of the process parameters and of the metal amount on the final properties of the particles (quantity, size, size distribution, oxidation state etc.,) was widely investigated. Moreover, the effect of the NPs on the photocatalytic activity of the resulting materials was evaluated for the case of the decomposition of stearic acid (SA) during UV-A irradiation. The reduction of the water contact angle (WCA) during the irradiation period was measured in order to test the photo-induced super-hydrophilicity (PSH). PMID:26716202

  10. Solid-phase photocatalytic degradation of polystyrene plastic with goethite modified by boron under UV-vis light irradiation

    NASA Astrophysics Data System (ADS)

    Liu, Guanglong; Zhu, Duanwei; Zhou, Wenbing; Liao, Shuijiao; Cui, Jingzhen; Wu, Kang; Hamilton, David

    2010-02-01

    A novel photodegradable polyethylene-boron-goethite (PE-B-goethite) composite film was prepared by embedding the boron-doped goethite into the commercial polyethylene. The goethite catalyst was modified by boron in order to improve its photocatalytic efficiency under the ultraviolet and visible light irradiation. Solid-phase photocatalytic degradation of the PE-B-goethite composite film was carried out in an ambient air at room temperature under ultraviolet and visible light irradiation. The properties of composite films were compared with those of the pure PE films and the PE-goethite composite films through performing weight loss monitoring, scanning electron microscope (SEM) analysis, FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS). The photo-induced degradation of PE-B-goethite composite films was higher than that of the pure PE films and the PE-goethite composite films under the UV-irradiation, while there has been little change under the visible light irradiation. The weight loss of the PE-B-goethite (0.4 wt.%) composite film reached 12.6% under the UV-irradiation for 300 h. The photocatalytic degradation mechanism of the composite films was briefly discussed.

  11. Preparation and photocatalytic activity of bicrystal phase TiO2 nanotubes containing TiO2-B and anatase

    NASA Astrophysics Data System (ADS)

    Huang, Chuanxi; Zhu, Kerong; Qi, Mengyao; Zhuang, Yonglong; Cheng, Chao

    2012-06-01

    Bicrystal phase TiO2 nanotubes (NTS) containing monoclinic TiO2-B and anatase were prepared by the hydrothermal reaction of anatase nanoparticles with NaOH aqueous solution and a heat treatment. Their structure was characterized by XRD, TEM and Raman spectra. The results showed that the bicrystal phase TiO2 NTS were formed after calcining H2Ti4O9·H2O NTS at 573 K. The bicrystal phase TiO2 NTS exhibit significantly higher photocatalytic activity than the single phase anatase NTS and Dessuga P-25 nanoparticles in the degradation of Methyl Orange aqueous solution under ultraviolet light irradiation, which is attributed to the large surface and interface areas of the bicrystal phase TiO2 NTS.

  12. Nanostructures and porous silicon: activity and phase transformation in sensors and photocatalytic reactors

    NASA Astrophysics Data System (ADS)

    Gole, James L.; Lewis, Stephen E.; Fedorov, Andrei; Prokes, Sharka

    2005-08-01

    Porous interfaces are being transformed within the framework of nanotechnology to develop highly efficient sensors, nanostructure modified microreactors, and active battery electrodes. We demonstrate the rapid and reversible sensing of HCl, NH3, CO, SO2, H2S, and NOx at or below the ppm level. Gold and tin-based nanostructured coatings are introduced to improve the detection of NH3, CO, and NOx as these coatings form the initial basis for introducing significant selectivity. These sensor suites are being extended to develop microreactors, with a goal to introduce quantum dot (QD) based photocatalysts within the porous interface structure. Highly efficient, visible light absorbing, anatase TiO2-xNx nanophotocatalysts have been formed in seconds at room temperature via the direct nitridation of anatase TiO2 nanocolloids. A tunability throughout the visible is found to depend upon the degree of nanoparticle agglomeration and upon the ready ability to seed these nanoparticles with metal (metal ions) including Pt, Co, and Ni. This metal ion seeding also leads to unique efficient phase transformations, including that of anatase to rutile TiO2, at room temperature. The visible light absorbing photocatalysts readily photodegrade methylene blue and gaseous ethylene. They can be transformed from liquids to gels and, in addition, can be placed on the surfaces of sensor and microreactor based configurations 1) to produce an improved photocatalytically induced solar based sensor response, and 2) with a goal to facilitate catalytically induced disinfection of airborne pathogens. In contrast to the nitridation process which is facile at the nanoscale, we find little or no direct nitridation of micrometer sized anatase or rutile TiO2 powders at room temperature. Thus, we illustrate an example of how a traversal to the nanoscale can vastly improve the efficiency for producing important submicron particles.

  13. GAS PHASE EXPOSURE HISTORY DERIVED FROM MATERIAL PHASE CONCENTRATION PROFILES USING SOLID PHASE MICRO-EXTRACTION

    EPA Science Inventory

    EPA Identifier: F8P31059
    Title: Gas Phase Exposure History Derived from Material Phase Concentration Profiles Using Solid Phase Micro-Extraction
    Fellow (Principal Investigator): Jonathan Lewis McKinney
    Institution: University of Missouri - ...

  14. Thermal phases of interstellar and quasar gas

    NASA Technical Reports Server (NTRS)

    Lepp, S.; Mccray, R.; Shull, J. M.; Woods, D. T.; Kallman, T.

    1985-01-01

    Interstellar gas may be in a variety of thermal phases, depending on how it is heated and ionized; here a unified picture of the equation of state of interstellar and quasar gas is presented for a variety of such mechanisms over a broad range of temperatures, densities, and column densities of absorbing matter. It is found that for select ranges of gas pressure, photoionizing flux, and heating, three thermally stable phases are allowed: coronal gas (T above 100,000 K); warm gas (T about 10,000 K); and cold gas (T less than 100 K). With attenuation of ultraviolet and X-ray radiation, the cold phase may undergo a transition to molecules. In quasar broad-line clouds, this transition occurs at column density N(H) = about 10 to the 23rd/sq cm and could result in warm molecular cores and observable emission from H2 and OH. The underlying atomic physics behind each of these phase transitions and their relevance to interstellar matter and quasars are discussed.

  15. Novel nano coordination polymer based synthesis of porous ZnO hexagonal nanodisk for higher gas sorption and photocatalytic activities

    NASA Astrophysics Data System (ADS)

    Rakibuddin, M.; Ananthakrishnan, Rajakumar

    2016-01-01

    Zinc(II)-based nano co-ordination polymers (NCPs) are first prepared at room temperature from three different isomers of dihydroxysalophen (DHS) ligand with Zn(OAc)2·2H2O and 1,4-benzenedicarboxylic acid (BDC) in DMF solvent. Facile calcinations of [Zn (DHS) (BDC)]·nH2O (shortly denoted as Zn(II)-based NCP) at ambient conditions produces porous ZnO hexagonal nanodisks. Moreover, a novel approach has been introduced to observe the effect of ligand of the NCP on the physico-chemical properties of the as-synthesized ZnO. The porous ZnO nanodisks are characterized by FT-IR, PXRD, TEM, FESEM, EDX and BET analysis, and the results exhibit that they possess different sizes, surface areas and porosities. Nitrogen gas sorption capacity and photocatalytic activities of the as-prepared ZnO nanodisks are also checked, and it is noticed that they differ in these physico-chemical properties due to having different porosities and surface areas. A comparative study is also done with commercially available ZnO; interestingly, the commercial ZnO exhibited lower surface area, gas sorption and photocatalytic activity compared to the ZnO nanodisks. Hence, preparation of the ZnO through the NCP route and tuning their physico-chemical properties would offer new directions in synthesis of various nano metal oxides of unique properties.

  16. Nitrogen-modified nano-titania: True phase composition, microstructure and visible-light induced photocatalytic NOx abatement

    NASA Astrophysics Data System (ADS)

    Tobaldi, D. M.; Pullar, R. C.; Gualtieri, A. F.; Otero-Irurueta, G.; Singh, M. K.; Seabra, M. P.; Labrincha, J. A.

    2015-11-01

    Titanium dioxide (TiO2) is a popular photocatalyst used for many environmental and anti-pollution applications, but it normally operates under UV light, exploiting ∼5% of the solar spectrum. Nitrification of titania to form N-doped TiO2 has been explored as a way to increase its photocatalytic activity under visible light, and anionic doping is a promising method to enable TiO2 to harvest visible-light by changing its photo-absorption properties. In this paper, we explore the insertion of nitrogen into the TiO2 lattice using our green sol-gel nanosynthesis method, used to create 10 nm TiO2 NPs. Two parallel routes were studied to produce nitrogen-modified TiO2 nanoparticles (NPs), using HNO3+NH3 (acid-precipitated base-peptised) and NH4OH (totally base catalysed) as nitrogen sources. These NPs were thermally treated between 450 and 800 °C. Their true phase composition (crystalline and amorphous phases), as well as their micro-/nanostructure (crystalline domain shape, size and size distribution, edge and screw dislocation density) was fully characterised through advanced X-ray methods (Rietveld-reference intensity ratio, RIR, and whole powder pattern modelling, WPPM). As pollutants, nitrogen oxides (NOx) are of particular concern for human health, so the photocatalytic activity of the NPs was assessed by monitoring NOx abatement, using both solar and white-light (indoor artificial lighting), simulating outdoor and indoor environments, respectively. Results showed that the onset of the anatase-to-rutile phase transformation (ART) occurred at temperatures above 450 °C, and NPs heated to 450 °C possessed excellent photocatalytic activity (PCA) under visible white-light (indoor artificial lighting), with a PCA double than that of the standard P25 TiO2 NPs. However, higher thermal treatment temperatures were found to be detrimental for visible-light photocatalytic activity, due to the effects of four simultaneous occurrences: (i) loss of OH groups and water adsorbed

  17. Electrothermal vaporization, part 1: gas phase chemistry

    NASA Astrophysics Data System (ADS)

    Majidi, Vahid; Xu, Ning; Smith, Robert G.

    2000-01-01

    This manuscript is the first of a two-part publication on evaluation of vaporization and atomization processes in electrothermal vaporizers (ETV). Part 1 is specifically focused on gas phase (and heterogeneous) chemistry in ETVs. Molecular absorption spectroscopy and thermogravimetric analysis (in conjunction with gas-phase mass spectrometry) are used to investigate the vaporization of Mg, Ca, Sr, Ba, Co and Ni (chloride and nitrate salts). Graphite, Pt, and Ta were used as substrate material for vaporizers to elucidate some observations of gas-phase chemistry. The experiments in Part I and II of this series are intentionally performed using wall vaporization to closely mimic the conditions used when ETV is employed as a sample introduction device.

  18. Surface modification of mixed-phase hydrogenated TiO2 and corresponding photocatalytic response

    NASA Astrophysics Data System (ADS)

    Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd; Juan, Joon Ching; Basirun, Wan Jefrey; Kandjani, Ahmad Esmaeiljadeh

    2015-12-01

    Preparation of highly photo-activated TiO2 is achievable by hydrogenation at constant temperature and pressure, with controlled hydrogenation duration. The formation of surface disorders and Ti3+ is responsible for the color change from white unhydrogenated TiO2 to bluish-gray hydrogenated TiO2. This color change, together with increased oxygen vacancies and Ti3+ enhanced the solar light absorption from UV to infra-red region. Interestingly, no band gap narrowing is observed. The photocatalytic activity in the UV and visible region is controlled by Ti3+ and oxygen vacancies respectively. Both Ti3+ and oxygen vacancies increases the electron density on the catalyst surface thus facilitates rad OH radicals formation. The lifespan of surface photo-excited electrons and holes are also sustained thus prevents charge carrier recombination. However, excessive amount of oxygen vacancies deteriorates the photocatalytic activity as it serves as charge traps. Hydrogenation of TiO2 also promotes the growth of active {0 0 1} facets and facilitates the photocatalytic activity by higher concentration of surface OH radicals. However, the growth of {0 0 1} facets is small and insignificant toward the overall photo-kinetics. This work also shows that larger role is played by Ti3+ and oxygen vacancies rather than the surface disorders created during the hydrogenation process. It also demonstrates the ability of hydrogenated TiO2 to absorb wider range of photons even though at a similar band gap as unhydrogenated TiO2. In addition, the photocatalytic activity is shown to be decreased for extended hydrogenation duration due to excessive catalyst growth and loss in the total surface area. Thus, a balance in the physico-chemical properties of hydrogenated TiO2 is crucial to enhance the photocatalytic activity by simply controlling the hydrogenation duration.

  19. Thermal evolution of structure and photocatalytic activity in polymer microsphere templated TiO2 microbowls

    NASA Astrophysics Data System (ADS)

    Erdogan, Deniz Altunoz; Polat, Meryem; Garifullin, Ruslan; Guler, Mustafa O.; Ozensoy, Emrah

    2014-07-01

    Polystyrene cross-linked divinyl benzene (PS-co-DVB) microspheres were used as an organic template in order to synthesize photocatalytic TiO2 microspheres and microbowls. Photocatalytic activity of the microbowl surfaces were demonstrated both in the gas phase via photocatalytic NO(g) oxidation by O2(g) as well as in the liquid phase via Rhodamine B degradation. Thermal degradation mechanism of the polymer template and its direct influence on the TiO2 crystal structure, surface morphology, composition, specific surface area and the gas/liquid phase photocatalytic activity data were discussed in detail. With increasing calcination temperatures, spherical polymer template first undergoes a glass transition, covering the TiO2 film, followed by the complete decomposition of the organic template to yield TiO2 exposed microbowl structures. TiO2 microbowl systems calcined at 600 °C yielded the highest per-site basis photocatalytic activity. Crystallographic and electronic properties of the TiO2 microsphere surfaces as well as their surface area play a crucial role in their ultimate photocatalytic activity. It was demonstrated that the polymer microsphere templated TiO2 photocatalysts presented in the current work offer a promising and a versatile synthetic platform for photocatalytic DeNOx applications for air purification technologies.

  20. Mixed phase lamellar titania-titanate anchored with Ag2O and polypyrrole for enhanced adsorption and photocatalytic activity.

    PubMed

    Kumar, Rajeev

    2016-09-01

    Ag2O/TiO2/polypyrrole composite was synthesized by stepwise modification of the rutile TiO2 though hydrothermal alkaline treatment to obtain mixed phase sodium titanate/titania (Na-TiO2) followed ion-exchange replacement of Na(+) by Ag(+) to get Ag2O/TiO2 (through precipitation) and H2O2 oxidative polymerization of pyrrole onto Ag2O/TiO2 to get final composite Ag2O/TiO2/polypyrrole (Ag2O/TiO2/PPY). Composite materials were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Field emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectroscopy (FTIR), Diffuse reflectance ultraviolet-visible spectroscopy (UV-vis DRS) and Raman analysis. The synthesized materials showed increase in the optical property, adsorption and photocatalytic scavenging of the methylene blue (MB). The adsorption capacity of MB onto the prepared materials was observed in the following order: TiO2photocatalytic decontamination of MB was as follows: TiO2photocatalytic decontamination was observed at pH 9. The kinetics studies revealed that the adsorption of MB followed the pseudo-first-order kinetic model. While kinetics for MB degradation were well defined by the Langmuir-Hinshelwood model at low and high concentrations. The obtained results demonstrate that the synergistic effect of adsorption and visible light photocatalysis is enough capable for 100% removal of MB from aquatic solution. PMID:27244593

  1. Continuous-Flow Gas-Phase Bioreactors

    NASA Technical Reports Server (NTRS)

    Wise, Donald L.; Trantolo, Debra J.

    1994-01-01

    Continuous-flow gas-phase bioreactors proposed for biochemical, food-processing, and related industries. Reactor contains one or more selected enzymes dehydrated or otherwise immobilized on solid carrier. Selected reactant gases fed into reactor, wherein chemical reactions catalyzed by enzyme(s) yield product biochemicals. Concept based on discovery that enzymes not necessarily placed in traditional aqueous environments to function as biocatalysts.

  2. Gas-Phase Infrared; JCAMP Format

    National Institute of Standards and Technology Data Gateway

    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.

  3. EPA GAS PHASE CHEMISTRY CHAMBER STUDIES

    EPA Science Inventory

    Gas-phase smog chamber experiments are being performed at EPA in order to evaluate a number of current chemical mechanisms for inclusion in EPA regulatory and research models. The smog chambers are 9000 L in volume and constructed of 2-mil teflon film. One of the chambers is co...

  4. Gas phase chemistry of the transactinides

    NASA Astrophysics Data System (ADS)

    Türler, A.

    1999-01-01

    In the past few years the gas phase chemistry of the first three transactinide elements rutherfordium (element 104), dubnium (element 105) and seaborgium (element 106) has been studied experimentally using OLGA, the On-line Gas chemistry Apparatus, developed at Paul Scherrer Institute. In each experiment, the investigated transactinide element was identified by measuring the characteristic decay properties of its isotopes. In the chemistry of rutherfordium and dubnium evidence for relativistic effects were found, as predicted previously in theoretical calculations. For the first time, the volatility of Sg oxychlorides in comparison to its lighter homologues W and Mo was measured. Also, the half-lives and SF-branches of the nuclides 265Sg and 266Sg were determined. Finally, prospects for a chemical separation of bohrium (element 107) and hassium (element 108) using gas phase chemistry will be discussed.

  5. Photocatalytic oxidation of methyl orange in a three-phase fluidized bed reactor.

    PubMed

    Nam, Wooseok; Kim, Jimin; Han, Guiyoung

    2002-06-01

    The photocatalytic oxidation of methyl orange under weak illumination conditions was carried out in two different types of fluidized bed reactors. TiO2 powder was employed as the photocatalysts and a 15 W low pressure mercury lamp was used as the light source and the reactor volume was 2.5 l. The parametric study of photocatalytic oxidation of methyl orange in two different types of fluidized beds was investigated; effect of catalyst loadings, pH, air flow rate, initial concentration and oxygen concentration on the oxidation reaction rate. The experimental results were analyzed in conjunction with the characteristics of fluidized bed and the reactor geometry effect on the reaction rate was analyzed. PMID:12108693

  6. Microemulsion-mediated solvothermal synthesis and photocatalytic properties of crystalline titania with controllable phases of anatase and rutile.

    PubMed

    Shen, Xiaojun; Zhang, Jinlong; Tian, Baozhu

    2011-08-30

    Titanium oxide with different ratios of anatase to rutile has been prepared by the microemulsion-mediated solvothermal method. The resulting samples were investigated by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, UV-vis diffuse reflectance spectra, transmission electron microscopy and Brunauer-Emmett-Teller analysis. The contents of anatase and rutile in the TiO(2) particles have been successfully controlled by simply adjusting the amount of urea in the aqueous phase of the microemulsion. Both the degradation of Rhodamine B in aqueous solutions and mineralization of TOC revealed that the catalyst containing 47.6% anatase have presented the highest photocatalytic activity. A proposed mechanism is discussed to interpret the evolution of the phases based on the effect of different amount of urea. PMID:21684078

  7. Efficient removal of toluene and benzene in gas phase by the TiO2/Y-zeolite hybrid photocatalyst.

    PubMed

    Takeuchi, Masato; Hidaka, Manabu; Anpo, Masakazu

    2012-10-30

    Efficient removal of toluene or benzene molecules thinly diffused in gas phase was achieved by using TiO(2)/Y-zeolite hybrid photocatalysts. TiO(2) of 10 wt% hybridized with a hydrophobic USY zeolite showed higher photocatalytic reactivity as compared to TiO(2) hybridized with hydrophilic H-Y or Na-Y zeolites. This phenomenon can be explained by the fact that the hydrophobic USY zeolite efficiently adsorbs the organic compounds and smoothly supplies them onto the TiO(2) photocatalyst surface. However, the toluene or benzene molecules, which are strongly trapped on the hydrophilic H(+) or Na(+) sites of zeolite, cannot diffuse onto the TiO(2) surfaces, resulting in lower photocatalytic reactivity. Although the adsorption capacity of the pure TiO(2) sample rapidly deteriorated, the TiO(2)/Y-zeolite hybrid system maintained a high adsorption efficiency to remove such aromatic compounds for a long period. PMID:22947182

  8. The effect of doping titanium dioxide nanoparticles on phase transformation, photocatalytic activity and anti-bacterial properties

    NASA Astrophysics Data System (ADS)

    Buzby, Scott Edward

    Nanosized titanium dioxide has a variety of important applications in everyday life including a photocatalyst for pollution remediation, photovoltaic devices, sunscreen, etc. This study focuses on the various properties of titanium dioxide nanoparticles doped with various cation and anion species. Samples were produced by various methods including metalorganic chemical vapor deposition (MOCVD), plasma assisted metalorganic chemical vapor deposition (PA-MOCVD) and sol-gel. Numerous techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron microscopy both scanning (SEM) and transmission (TEM) were used for physical characterization. Photocatalytic properties were determined by the oxidation of methylene blue dye and 2-chlorophenol in water as well as gaseous formic acid with results analyzed by high performance liquid chromatography (HPLC), Fourier transform infrared spectroscopy (FTIR) and ultra violet - visible spectroscopy (UV-VIS). For the purpose of enhancement of the photocatalytic activity of titanium dioxide nanoparticles, the effect of anion doping and the anatase-rutile phase ratio were studied. Although anatase, rutile and mixed crystallite phases all show some degree of activity in photocatalytic reactions, these results show that anatase is better suited for the degradation of organic compounds in an aqueous medium any advantage in photocatalytic activity gained through the enhancement in optical response from the smaller band gap by addition of rutile was overcome by the negatives associated with the rutile phase. Furthermore substitutional nitrogen doping showed significant improvement in UV photocatalysis as well as allowing for visible light activation of the catalyst. Further studies on the phase transitions in titanium dioxide nanoparticles were carried out by synthesizing various cation doped samples by sol-gel. Analysis of the phases by XRD showed an inverse relationship between dopant size and rutile percentage

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

    NASA Astrophysics Data System (ADS)

    Qazi, H. I. A.; Nie, Qiu-Yue; Li, He-Ping; Zhang, Xiao-Fei; Bao, Cheng-Yu

    2015-12-01

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

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

    SciTech Connect

    Qazi, H. I. A.; Li, He-Ping Zhang, Xiao-Fei; Bao, Cheng-Yu; Nie, Qiu-Yue

    2015-12-15

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

  11. Centrifugal Liquid/Gas Separator With Phase Detectors

    NASA Technical Reports Server (NTRS)

    Schneider, Steven J.

    1994-01-01

    Centrifugal liquid/gas separator that includes phase (liquid or gas) detectors helps ensure exclusiveness of each phase at its assigned outlet. Acoustic sensors in centrifugal liquid/gas separator measure speeds of sound in nominally pure liquid and nominally pure gas at liquid and gas outlets respectively. When speed of sound is that of pure liquid or gas, valve opens to let liquid or gas flow out.

  12. Receptors useful for gas phase chemical sensing

    DOEpatents

    Jaworski, Justyn W; Lee, Seung-Wuk; Majumdar, Arunava; Raorane, Digvijay A

    2015-02-17

    The invention provides for a receptor, capable of binding to a target molecule, linked to a hygroscopic polymer or hydrogel; and the use of this receptor in a device for detecting the target molecule in a gaseous and/or liquid phase. The invention also provides for a method for detecting the presence of a target molecule in the gas phase using the device. In particular, the receptor can be a peptide capable of binding a 2,4,6-trinitrotoluene (TNT) or 2,4,-dinitrotoluene (DNT).

  13. Colloidal nanocrystals of orthorhombic Cu2ZnGeS4: phase-controlled synthesis, formation mechanism and photocatalytic behavior

    NASA Astrophysics Data System (ADS)

    Fan, Cong-Min; Regulacio, Michelle D.; Ye, Chen; Lim, Suo Hon; Lua, Shun Kuang; Xu, Qing-Hua; Dong, Zhili; Xu, An-Wu; Han, Ming-Yong

    2015-02-01

    The orthorhombic polymorph of Cu2ZnGeS4 (CZGS) is a metastable wurtzite-derived phase that can only be prepared in the bulk form by extensive heating at high temperatures (>=790 °C) when using the conventional solid-state reaction route. By employing a facile solution-based synthetic strategy, we were able to obtain phase-pure orthorhombic CZGS in nanocrystalline form at a much lower reaction temperature. Prior to this work, the colloidal synthesis of single-phase orthorhombic CZGS on the nanoscale has never been reported. We find that the use of an appropriate combination of coordinating solvents and precursors is crucial to the sole formation of this metastable phase in solution. A possible formation mechanism is proposed on the basis of our experimental results. Because CZGS consists of environmentally benign metal components, it is regarded as a promising alternative material to the technologically useful yet toxic cadmium-containing semiconductors. The orthorhombic CZGS nanocrystals display strong photon absorption in the visible spectrum and are photocatalytically active in dye degradation under visible-light illumination.The orthorhombic polymorph of Cu2ZnGeS4 (CZGS) is a metastable wurtzite-derived phase that can only be prepared in the bulk form by extensive heating at high temperatures (>=790 °C) when using the conventional solid-state reaction route. By employing a facile solution-based synthetic strategy, we were able to obtain phase-pure orthorhombic CZGS in nanocrystalline form at a much lower reaction temperature. Prior to this work, the colloidal synthesis of single-phase orthorhombic CZGS on the nanoscale has never been reported. We find that the use of an appropriate combination of coordinating solvents and precursors is crucial to the sole formation of this metastable phase in solution. A possible formation mechanism is proposed on the basis of our experimental results. Because CZGS consists of environmentally benign metal components, it is

  14. Gas phase chemistry of chlorine nitrate

    SciTech Connect

    Okumura, M.; Moore, T.A.; Crellin, K.C.

    1995-12-31

    Chlorine nitrate (ClONO{sub 2}) is a reservoir of both ClO{sub x} and NO{sub x} radicals in Earth`s stratosphere, and its decomposition is important in determining the abundance of stratospheric ozone. We present experimental and theoretical studies that explore the mechanisms and dynamics of processes leading to ClONO{sub 2} destruction in the stratosphere. Molecular beam photodissociation experiments have been performed to determine the decomposition pathways of ClONO{sub 2} upon excitation at 308 nm and to explore the possibility of a long-lived excited state. We have also investigated the reaction of chlorine nitrate with chloride ions Cl{sup -} in the gas phase. The gas phase ionic reaction may elucidate ionic mechanisms of heterogeneous reactions occurring on the surfaces of Polar Stratospheric Cloud particles and also raise doubts about proposed schemes to mitigate ozone depletion by electrifying the stratosphere.

  15. The gas-phase acidity of nitrocyclopropane

    NASA Astrophysics Data System (ADS)

    Bartmess, John E.; Wilson, Burton; Sorensen, Daniel N.; Bloor, John E.

    1992-09-01

    Nitrocyclopropane is 10.5 kcal mol-1 weaker as an acid in the gas phase than its open-chain analog, 2-nitropropane. This is attributed to the conflicting hybridization requirements for carbanion stabilization by the cyclopropyl ring and by the nitro group. Based on reactivities, the deprotonated form does not ring-open to either the 2-nitroallyl anion or the 1-nitroallyl anion.

  16. Gas-Phase Photoionization Of A Protein

    NASA Astrophysics Data System (ADS)

    Milosavljevic, A. R.; Giuliani, A.; Nicolas, C.; Gil, J.-F.; Lemaire, J.; Refregiers, M.; Nahon, L.

    2010-07-01

    We present preliminary results on gas phase photoionization of electrosprayproduced multiply protonated cytochrome c protein (104 amino acids; ˜12.4 kDa), which has been achieved with a newly developed experimental system for spectroscopy of electrosprayed ions in a linear quadrupole ion trap using a monochromatized vacuum ultraviolet (VUV) synchrotron radiation and tandem mass spectrometry method. The investigation of proteins in the gas phase, where they are free of the influence of counterions and solvent molecules, offer a possibility to understand their intrinsic molecular properties. However, due to limited both ion densities and available number of photons, the use of synchrotron radiation for the trapped ions spectroscopy is a rather challenging task. The feasibility of coupling a Fourier transform ion cyclotron resonance ion trap with soft x-ray synchrotron beamline and the first successful use of synchrotron radiation for spectroscopy of electrosprayed negative ions stored in a three-dimensional quadrupole ion trap have been demonstrated only recently (R. Thissen et al., 2008, Phys. Rev. Lett., 100, 223001; A. Giulliani et al., Proc. 57th ASMS Conf., Philadelphia, 2009). The present results are the first reported on photoionization of kDa species in the gas phase and are valuable regarding both a fundamental interest of accessing physical properties of large biological ions isolated in vacuo and potential development of a new technique for proteomics.

  17. Intensification of gas-phase photoxidative dehydrogenation of ethanol to acetaldehyde by using phosphors as light carriers.

    PubMed

    Ciambelli, P; Sannino, D; Palma, V; Vaiano, V; Mazzei, R S

    2011-03-01

    In this work a significant improvement of VO(x)/TiO(2) photocatalytic activity in the selective partial oxidation of ethanol to acetaldehyde was achieved by the simultaneous irradiation with light emitting phosphorescent particles and UVA-LEDs as external light source. Photocatalytic tests were carried out in a gas-solid photocatalytic fluidized bed reactor at high illumination efficiency, in which the bed is constituted by VO(x)/TiO(2) photocatalyst at nominal V(2)O(5) content of 5 wt% and suitable selected phosphors, diluted with glass spheres. In this way, phosphors were fluidized together with the catalyst, excited by external UVA-LEDs, emitting their stored energy in close proximity to the catalyst. In the absence of phosphors the ethanol consumption rate initially grows linearly with initial alcohol concentration, then bends towards an asymptotic value for initial ethanol concentration higher than 0.5 vol%. By contrast, when phosphors are present, the ethanol consumption rate increased linearly in the overall range. In all cases acetaldehyde was the main product detected in gas phase with a selectivity of about 97%, ethylene and carbon dioxide the by-products. The results evidenced that the presence of phosphors allowed improved photon transfer, increasing the apparent quantum yield from 2 to 30% together with a high photoreactivity. PMID:20953515

  18. Phase transformation-induced crystal plane effect of iron oxide micropine dendrites on gaseous toluene photocatalytic oxidation

    NASA Astrophysics Data System (ADS)

    Wu, Hongjing; Wang, Liuding

    2014-01-01

    Hematite (α-Fe2O3), magnetite (Fe3O4), and maghemite (γ-Fe2O3) micropine dendrites were synthesized by a facile hydrothermal method and oxidation-reduction process. The samples have been thoroughly characterized by various physicochemical techniques. The adsorption ability, quantum efficiency, and the photo-induced charge separation of the electron-hole pair in the samples were demonstrated by the XPS, FTIR, UV-vis, and PL spectroscopy. The α-Fe2O3 showed higher catalytic activity than the other two samples for photocatalytic oxidation of gaseous toluene. This may be attributed to the phase transformation-induced crystal plane effect of the α-Fe2O3 micropine dendrite, which has relatively more reactive crystal planes {0 0 1} and {1 1 0} exposed on the surface of α-Fe2O3.

  19. Photocatalytic activity of a hierarchically macro/mesoporous titania.

    PubMed

    Wang, Xinchen; Yu, Jimmy C; Ho, Chunman; Hou, Yidong; Fu, Xianzhi

    2005-03-15

    Light-harvesting macroporous channels have been successfully incorporated into a mesoporous TiO(2) framework to increase its photocatalytic activity. This bimodal porous material was characterized by X-ray diffractometry in both low-angle and wide-angle ranges, N(2) adsorption-desorption analysis, scanning and transmission electron microscopy, FT-IR, and diffuse reflectance spectroscopy. Ethylene photodegradation in gas-phase medium was employed as a probe reaction to evaluate the photocatalytic reactivity of the catalysts. The results reveal that sintering temperature significantly affects the structural stability and photocatalytic activity of titania. The catalyst which calcined at 350 degrees C possessed an intact macro/mesoporous structure and showed photocatalytic reactivity about 60% higher than that of commercial P25 titania. When the sample was calcined at 500 degrees C, the macroporous structure was retained but the mesoporous structure was partly destroyed. Further heating at temperatures above 600 degrees C destroyed both macro- and mesoporous structures, accompanied by a loss in photocatalytic activity. The high photocatalytic performance of the intact macro/mesoporous TiO(2) may be explained by the existence of macrochannels that increase photoabsorption efficiency and allow efficient diffusion of gaseous molecules. PMID:15752052

  20. Photocatalytic characteristics of single phase Fe-doped anatase TiO{sub 2} nanoparticles sensitized with vitamin B{sub 12}

    SciTech Connect

    Gharagozlou, Mehrnaz; Bayati, R.

    2015-01-15

    Highlights: • Anatase TiO{sub 2}/B{sub 12} hybrid nanostructured catalyst was successfully synthesized by sol–gel technique. • The nanoparticle catalyst was doped with iron at several concentrations. • Nanoparticles were characterized in detail by XRD, Raman, TEM, EDS, and spectroscopy techniques. • The formation mechanism and role of point defects on photocatalytic properties were discussed. • A structure-property-processing correlation was established. - Abstract: We report a processing-structure-property correlation in B{sub 12}-anatase titania hybrid catalysts doped with several concentrations of iron. Our results clearly show that low-level iron doping alters structure, defect content, and photocatalytic characteristics of TiO{sub 2}. XRD and Raman studies revealed formation of a single-phase anatase TiO{sub 2} where no iron based segregation in particular iron oxide, was detected. FT-IR spectra clearly confirmed sensitization of TiO{sub 2} nanoparticles with vitamin B{sub 12}. TEM micrographs and diffraction patterns confirmed crystallization of anatase nanoparticles with a radius of 15–20 nm. Both XRD and Raman signals showed a peak shift and a peak broadening which are surmised to originate from creation of point defects, namely oxygen vacancy and titanium interstitial. The doped samples revealed a narrower band gap as compared to undoped samples. Photocatalytic activity of the samples was assessed through measuring the decomposition rate of rhodamine B. It was found that sensitization with vitamin B{sub 12} and Fe-doping significantly enhances the photocatalytic efficiency of the anatase nanoparticles. We also showed that there is an optimum Fe-doping level where the maximum photocatalytic activity is achieved. The boost of photocatalytic activity was qualitatively understood to originate from a more effective use of the light photons, formation of point defects, which enhance the charge separation, higher carrier mobility.

  1. Photocatalytic degradation of trichloroethylene in aqueous phase using nano-ZNO/Laponite composites.

    PubMed

    Joo, Jin Chul; Ahn, Chang Hyuk; Jang, Dae Gyu; Yoon, Young Han; Kim, Jong Kyu; Campos, Luiza; Ahn, Hosang

    2013-12-15

    The feasibility of nano-ZnO/Laponite composites (NZLc) as a valid alternative to TiO2 to mineralize trichloroethylene (TCE) without difficulties for recovery of photocatalysts was evaluated. Based on the experimental observations, the removal of TCE using NZLc under UV irradiation was multiple reaction processes (i.e., sorption, photolysis, and photocatalysis). Sorption of TCE was thermodynamically favorable due to the hydrophobic partitioning into crosslinked poly vinyl alcohol, and the adsorption onto high-surface-area mineral surfaces of both ZnO and Laponite. The degradation efficiency of TCE can be significantly improved using NZLc under UV irradiation, indicating that ZnO-mediated heterogeneous photocatalytic degradation occurred. However, the degradation efficiency was found to vary with experimental conditions (e.g., initial concentration of TCE, loading amount of NZLc, the intensity of light and initial solution pH). Although the removal of TCE by NZLc was found to be a complex function of sorption, photolysis, and photocatalysis, the photocatalytic degradation of TCE on the surface of ZnO was critical. Consequently, developed NZLc can be applied as a valid alternative to suspended TiO2 powder, and overcome drawbacks (e.g., filtration and recovery of photocatalysts) in degradation of TCE for various water resources. PMID:24239256

  2. Structural, morphological, gas sensing and photocatalytic characterization of MoO3 and WO3 thin films prepared by the thermal vacuum evaporation technique

    NASA Astrophysics Data System (ADS)

    Arfaoui, A.; Touihri, S.; Mhamdi, A.; Labidi, A.; Manoubi, T.

    2015-12-01

    Thin films of molybdenum trioxide and tungsten trioxide were deposited on glass substrates using a simplified thermal evaporation under vacuum method monitored by heat treatment in flowing oxygen at 500 °C for 1 h. The structural and morphological properties of the films were investigated using X-ray diffraction, Raman spectroscopy, atomic force microscopy and scanning electron microscopy. The X-ray diffraction analysis shows that the films of MoO3 and WO3 were well crystallized in orthorhombic and monoclinic phase respectively with the crystallites preferentially oriented toward (2 0 0) direction parallel a-axis for both samples. In literature, we have shown in previous papers that structural and surface morphology of metal thin films play an important role in the gas detection mechanism. In this article, we have studied the response evolution of MoO3 and WO3 thin films sensors ethanol versus time, working temperature and the concentration of the ethanol. It was found that these films had high sensitivity to ethanol, which made them as a good candidate for the ethanol sensor. Finally, the photocatalytic activity of the samples was evaluated with respect to the degradation reaction of a wastewater containing methylene blue (MB) under UV-visible light irradiation. The molybdenum trioxide exhibits a higher degradation rate than the tungsten trioxide thin films under similar experimental conditions.

  3. Solar Photocatalytic Hydrogen Production from Water Using a Dual Bed Photosystem - Phase I Final Report and Phase II Proposal

    SciTech Connect

    Clovis A. Linkous; Darlene K. Slattery

    2000-09-11

    In this work we are attempting to perform the highly efficient storage of solar energy in the form of H{sub 2} via photocatalytic decomposition of water. While it has been demonstrated that H{sub 2} and O{sub 2} can be evolved from a single vessel containing a single suspended photocatalyst (Sayama 1994; 1997), we are attempting to perform net water-splitting by using two photocatalysts immobilized in separate containers, or beds. A schematic showing how the device would work is shown.

  4. Colloidal nanocrystals of orthorhombic Cu2ZnGeS4: phase-controlled synthesis, formation mechanism and photocatalytic behavior.

    PubMed

    Fan, Cong-Min; Regulacio, Michelle D; Ye, Chen; Lim, Suo Hon; Lua, Shun Kuang; Xu, Qing-Hua; Dong, Zhili; Xu, An-Wu; Han, Ming-Yong

    2015-02-21

    The orthorhombic polymorph of Cu2ZnGeS4 (CZGS) is a metastable wurtzite-derived phase that can only be prepared in the bulk form by extensive heating at high temperatures (≥790 °C) when using the conventional solid-state reaction route. By employing a facile solution-based synthetic strategy, we were able to obtain phase-pure orthorhombic CZGS in nanocrystalline form at a much lower reaction temperature. Prior to this work, the colloidal synthesis of single-phase orthorhombic CZGS on the nanoscale has never been reported. We find that the use of an appropriate combination of coordinating solvents and precursors is crucial to the sole formation of this metastable phase in solution. A possible formation mechanism is proposed on the basis of our experimental results. Because CZGS consists of environmentally benign metal components, it is regarded as a promising alternative material to the technologically useful yet toxic cadmium-containing semiconductors. The orthorhombic CZGS nanocrystals display strong photon absorption in the visible spectrum and are photocatalytically active in dye degradation under visible-light illumination. PMID:25619770

  5. Morphology-modulation of SnO2 Hierarchical Architectures by Zn Doping for Glycol Gas Sensing and Photocatalytic Applications

    PubMed Central

    Zhao, Qinqin; Ju, Dianxing; Deng, Xiaolong; Huang, Jinzhao; Cao, Bingqiang; Xu, Xijin

    2015-01-01

    The morphology of SnO2 nanospheres was transformed into ultrathin nanosheets assembled architectures after Zn doping by one-step hydrothermal route. The as-prepared samples were characterized in detail by various analytical techniques including scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and nitrogen adsorption-desorption technique. The Zn-doped SnO2 nanostructures proved to be the efficient gas sensing materials for a series of flammable and explosive gases detection, and photocatalysts for the degradation of methyl orange (MO) under UV irradiation. It was observed that both of the undoped and Zn-doped SnO2 after calcination exhibited tremendous gas sensing performance toward glycol. The response (S = Ra/Rg) of Zn-doped SnO2 can reach to 90 when the glycol concentration is 100 ppm, which is about 2 times and 3 times higher than that of undoped SnO2 sensor with and without calcinations, respectively. The result of photocatalytic activities demonstrated that MO dye was almost completely degraded (~92%) by Zn-doped SnO2 in 150 min, which is higher than that of others (MO without photocatalyst was 23%, undoped SnO2 without and with calcination were 55% and 75%, respectively). PMID:25597269

  6. Gas phase thermochemistry of organogermanium compounds

    SciTech Connect

    Engel, J.P.

    1993-12-07

    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: {alpha}-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.

  7. A comparative study of optical absorption and photocatalytic properties of nanocrystalline single-phase anatase and rutile TiO{sub 2} doped with transition metal cations

    SciTech Connect

    Kernazhitsky, L.; Shymanovska, V.; Gavrilko, T.; Naumov, V.; Kshnyakin, V.; Khalyavka, T.

    2013-02-15

    The effect of nanocrystalline TiO{sub 2} doping with transition metal cations (Cu{sup 2+}, Fe{sup 3+}, Co{sup 2+}, Cr{sup 3+}) on their optical absorption and photocatalytic properties was investigated. The obtained metal-doped TiO{sub 2} samples were characterized by X-ray diffraction, scanning electron microscopy, and UV-vis absorption spectroscopy. It is shown that doping effect on anatase (A) and rutile (R) properties is quite different, being much stronger and complicated on A than on R. Contrary to doped R, doped A revealed a significant red shift of the absorption edge along with the band gap narrowing. Photocatalytic activity of anatase increases upon doping in the order: Aphotocatalytic activity of rutile samples decreases upon doping in the series R>R/Co>R/Cu>R/Fe>R/Cr, indicating the inhibitory effect of impurity cations. This fact correlates with the decrease in the UV absorption of the doped rutile in the region of the Hg-lamp irradiation at 4.88 eV. - Graphical abstract: A red shift of the absorption edge of nanocrystalline single-phase anatase after doping with transition metal cations. Highlights: Black-Right-Pointing-Pointer Single-phase anatase and rutile powders surface-doped with transition metal cations. Black-Right-Pointing-Pointer Absorption edge and band gap of rutile do not change with surface doping. Black-Right-Pointing-Pointer Band gap of surface-doped anatase reduces being the lowest for A/Fe. Black-Right-Pointing-Pointer The surface-doping improves photocatalytic activity of anatase. Black-Right-Pointing-Pointer The surface-doping inhibits photocatalytic activity of rutile.

  8. Vaccum Gas Tungsten Arc Welding, phase 1

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

    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.

  9. Conversion of nitrogen oxides on commercial photocatalytic dispersion paints

    NASA Astrophysics Data System (ADS)

    Laufs, S.; Burgeth, G.; Duttlinger, W.; Kurtenbach, R.; Maban, M.; Thomas, C.; Wiesen, P.; Kleffmann, J.

    2010-06-01

    In the present study, photocatalytic reactions of nitrogen oxides (NO x = NO + NO 2) were studied on commercial TiO 2 doped facade paints in a flow tube photoreactor under simulated atmospheric conditions. Fast photocatalytic conversion of NO and NO 2 was observed only for the photocatalytic paints and not for non-catalytic reference paints. Nitrous acid (HONO) was formed in the dark on all paints studied, however, it efficiently decomposes under irradiation only on the photocatalytic samples. Thus, it is concluded that photocatalytic paint surfaces do not represent a daytime source of HONO, in contrast to other recent studies on pure TiO 2 surfaces. As main final product, the formation of adsorbed nitric acid/nitrate anion (HNO 3/NO 3-) was observed with near to unity yield. In addition, traces of H 2O 2 were observed in the gas phase only in the presence of O 2. Formation of the greenhouse gas nitrous oxide (N 2O) could be excluded. The uptake kinetics of NO, NO 2 and HONO was very fast under atmospheric conditions (e.g. γ(NO + TiO 2) > 10 -5). Thus, the uptake on urban surfaces (painted houses, etc.) will be limited by transport. For a hypothetically painted street canyon, an average reduction of nitrogen oxide levels of ca. 5% is estimated. Since the harmful HNO 3/NO 3- is formed on the surface of the photoactive paints, whereas it is formed in the gas phase in the atmosphere, the use of photocatalytic paints may also help to reduce acid deposition, e.g. on plants, or nitric acid related health issues.

  10. Giddings Austin chalk enters deep lean-gas phase

    SciTech Connect

    Moritis, G.

    1995-12-25

    Deep lean gas is the latest phase in the growth of the Giddings field Austin chalk play. The first phase involved drilling vertical oil and gas wells. Next came the horizontal well boom in the shallower Austin chalk area, which is still continuing. And now this third phase places horizontal laterals in the Austen chalk at about 14,000--15,000 ft to produce lean gas. The article describes the producing wells and gas gathering.

  11. Simultaneous SO2 and NO removal from flue gas based on TiO2 photocatalytic oxidation.

    PubMed

    Zhao, Yi; Han, Jing; Shao, Yuan; Feng, Yana

    2009-12-14

    A new approach to the simultaneous removal of SO2 and NO from flue gas, by TiO2 photocatalysis based on UV irradiation technology, is presented. Experiments on the simultaneous desulphurization and denitrification were carried out using this photocatalyst in a self-designed photocatalytic reactor. Under the optimal experimental conditions, a removal efficiency of 98% for SO2 and 50% for NO was achieved. Scanning electron microscopy, transmission electron microscopy and X-ray energy spectrometry were used to observe the surface characteristics of the TiO2 photocatalyst. It was found that the surface of the quartz sand carrier was covered with Ti, on which the Si content of the quartz sand carrier was similar to the Ti content, indicating that the quartz sand supported the TiO2 membrane well. Based on the results of X-ray photoelectron spectroscopy (XPS) and chemical analysis of the resulting products, the SO2 and NO removal mechanisms were revealed. Sulphate was the main desulphurization product and nitrite was the main denitrification product. In the removal reaction, NO was rapidly oxidized to NO2 and absorbed in the chemical reaction. PMID:20184000

  12. Base pair analogs in the gas phase.

    PubMed

    Roscioli, Joseph R; Pratt, David W

    2003-11-25

    A rotationally resolved electronic spectrum of the gas-phase dimer 2-aminopyridine.2-pyridone, an analog of the adenine.thymine base pair, has been observed and assigned, leading to precise measurements of its moments of inertia and preliminary determinations of its structure. A Watson-Crick configuration results, with N...H-N and N-H...O hydrogen bond lengths of 2.898 and 2.810 A, respectively. The two bases are found not to be coplanar; a dihedral angle of 6.1 degrees between the base planes is also estimated from the measured moments of inertia. Possible chemical and biological implications of these results are discussed. PMID:14612563

  13. Phase ordering kinetics of the Bose gas

    SciTech Connect

    Damle, K.; Majumdar, S.N.; Sachdev, S.

    1996-12-01

    We study the approach to equilibrium of a Bose gas to a superfluid state. We point out that dynamic scaling, characteristic of far from equilibrium phase-ordering systems, should hold. We stress the importance of a nondissipative Josephson precession term in driving the system to a new universality class. A model of coarsening in dimension {ital d}=2, involving a quench between two temperatures below the equilibrium superfluid transition temperature ({ital T}{sub {ital c}}), is exactly solved and demonstrates the relevance of the Josephson term. Numerical results on quenches from above {ital T}{sub {ital c}} in {ital d}=2,3 provide evidence for the scaling picture postulated. {copyright} {ital 1996 The American Physical Society.}

  14. Phase transitions in a gas of anyons

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

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

  15. Phase transitions in a gas of anyons

    SciTech Connect

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

    2010-10-01

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

  16. Gas-phase protonation thermochemistry of adenosine.

    PubMed

    Touboul, David; Bouchoux, Guy; Zenobi, Renato

    2008-09-18

    The goal of this work was to obtain a detailed insight on the gas-phase protonation energetic of adenosine using both mass spectrometric experiments and quantum chemical calculations. The experimental approach used the extended kinetic method with nanoelectrospray ionization and collision-induced dissociation tandem mass spectrometry. This method provides experimental values for proton affinity, PA(adenosine) = 979 +/- 1 kJ.mol (-1), and for the "protonation entropy", Delta p S degrees (adenosine) = S degrees (adenosineH +) - S degrees (adenosine) = -5 +/- 5 J.mol (-1).K (-1). The corresponding gas-phase basicity is consequently equal to: GB(adenosine) = 945 +/- 2 kJ.mol (-1) at 298K. Theoretical calculations conducted at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p) level, including 298 K enthalpy correction, predict a proton affinity value of 974 kJ.mol (-1) after consideration of isodesmic proton transfer reactions with pyridine as the reference base. Moreover, computations clearly showed that N3 is the most favorable protonation site for adenosine, due to a strong internal hydrogen bond involving the hydroxyl group at the 2' position of the ribose sugar moiety, unlike observations for adenine and 2'-deoxyadenosine, where protonation occurs on N1. The existence of negligible protonation entropy is confirmed by calculations (theoretical Delta p S degrees (adenosine) approximately -2/-3 J.mol (-1).K (-1)) including conformational analysis and entropy of hindered rotations. Thus, the calculated protonation thermochemical properties are in good agreement with our experimental measurements. It may be noted that the new PA value is approximately 10 kJ.mol (-1) lower than the one reported in the National Institute of Standards and Technology (NIST) database, thus pointing to a correction of the tabulated protonation thermochemistry of adenosine. PMID:18720985

  17. Transferring pharmaceuticals into the gas phase

    NASA Astrophysics Data System (ADS)

    Christen, Wolfgang; Krause, Tim; Rademann, Klaus

    2008-11-01

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

  18. Influences of TiO2 phase structures on the structures and photocatalytic hydrogen production of CuOx/TiO2 photocatalysts

    NASA Astrophysics Data System (ADS)

    Liu, Yuanxu; Wang, Zhonglei; Huang, Weixin

    2016-12-01

    CuOx/TiO2 photocatalysts employing TiO2 with different phase structures as well as P25 as supports were prepared, and their structures and activity for photocatalytic H2 production in methanol/water solution under simulated solar light were comparatively studied. Structural characterization results demonstrated that the TiO2 phase structure strongly affects the CuOx-TiO2 interaction and copper species in various CuOx/TiO2 photocatalysts. The Cu2O-rutile TiO2 interaction is much stronger than the Cu2O-anatase TiO2 interaction, facilitates the interfacial charge transfer process within the Cu2O-rutile TiO2 heterojunction but disables supported Cu2O to catalyze the hole-participated methanol oxidation. The Cu2O-anatase TiO2 heterojunction with the appropriate Cu2O-anatase TiO2 interaction and thus the balancing efficiencies between the interfacial charge transfer process and hole-participated methanol oxidation is most photocatalytic active, and CuOx/P25 with the largest population of Cu2O-anatase TiO2 heterojunction exhibits the highest photocatalytic H2 production. These results provide novel insights in the applied surface science of CuOx/TiO2 photocatalysts.

  19. (0 0 1) Facet-exposed anatase-phase TiO2 nanotube hybrid reduced graphene oxide composite: Synthesis, characterization and application in photocatalytic degradation

    NASA Astrophysics Data System (ADS)

    Zhou, Xun; Shi, Tiejun; Wu, Jing; Zhou, Haiou

    2013-12-01

    Reduced graphene oxide (RGO) and TiO2 nanotube (TNT) with (0 0 1) facet-exposed anatase phase are covalently bonded together to synthesize TNT hybrid RGO (RGO-TNT) through consecutive process such as hydrothermal reaction, HCl washing, lyophilization and heat treatment with graphene oxide (GO), TiO2 powder and high concentration NaOH solution as the starting materials. The TNT with the diameter between 10 and 20 nm characterized by high resolution transmission electron microscopy (HRTEM) is in anatase phase proven by X-ray diffraction (XRD) and HRTEM. Additionally, the more active (0 0 1) facet is exposed identified by HRTEM. More significantly, TNT is bridged to RGO by Csbnd Ti bond by the measurement of X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) spectra has testified that RGO in RGO-TNT can transfer and accept photoelectrons from TNT. The photocatalytic activity of RGO-TNT for degrading methylene blue (MB) is enhanced by contrast with pure TNT, and changeable by adjusting the mass ratios of GO to TiO2 powder. Simultaneously, lyophilization is benefit for maintaining the high active surface area of RGO-TNT, which is deeply in relationship with a higher photocatalytic activity. After four running cycles of photocatalytic degradation, RGO-TNT has shown a high stability and perfect reproducibility.

  20. Phase transformations during HLnTiO4 (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

    NASA Astrophysics Data System (ADS)

    Silyukov, Oleg I.; Abdulaeva, Liliia D.; Burovikhina, Alena A.; Rodionov, Ivan A.; Zvereva, Irina A.

    2015-03-01

    Layered HLnTiO4 (Ln=La, Nd) compounds belonging to Ruddlesden-Popper phases were found to form partially hydrated compounds Ln2Ti2O7·xH2O during thermal dehydration as well as defect oxides Ln2□Ti2O7 as final products. Further heating of metastable defect Ln2□Ti2O7 substances leads to the formation of pyrochlore-type oxides Ln2Ti2O7 (p), with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln2Ti2O7. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO4

  1. Gas: A Neglected Phase in Remediation of Metals and Radionuclides

    SciTech Connect

    Denham, Miles E.; Looney, Brian B

    2005-09-28

    The gas phase is generally ignored in remediation of metals and radionuclides because it is assumed that there is no efficient way to exploit it. In the literal sense, all remediations involve the gas phase because this phase is linked to the liquid and solid phases by vapor pressure and thermodynamic relationships. Remediation methods that specifically use the gas phase as a central feature have primarily targeted volatile organic contaminants, not metals and radionuclides. Unlike many organic contaminants, the vapor pressure and Henry's Law constants of metals and radionuclides are not generally conducive to direct air stripping of dissolved contaminants. Nevertheless, the gas phase can play an important role in remediation of inorganic contaminants and provide opportunities for efficient, cost effective remediation. The objective here is to explore ways in which manipulation of the gas phase can be used to facilitate remediation of metals and radionuclides.

  2. Phase transformations during HLnTiO{sub 4} (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

    SciTech Connect

    Silyukov, Oleg I. Abdulaeva, Liliia D.; Burovikhina, Alena A.; Rodionov, Ivan A.; Zvereva, Irina A.

    2015-03-15

    Layered HLnTiO{sub 4} (Ln=La, Nd) compounds belonging to Ruddlesden–Popper phases were found to form partially hydrated compounds Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O during thermal dehydration as well as defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7} as final products. Further heating of metastable defect Ln{sub 2}□Ti{sub 2}O{sub 7} substances leads to the formation of pyrochlore-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}photocatalytic activity in the order of HLnTiO{sub 4}photocatalytic activity of all obtained compounds. The hydrogen evolution rate increased in the course of the structure changes during thermolysis.

  3. Gas phase atomic and molecular processes

    NASA Astrophysics Data System (ADS)

    Zhu, Cheng

    . that in interstellar clouds HF is the major form of gas phase fluorine.

  4. Gas-phase basicity of 2-furaldehyde.

    PubMed

    Ricci, Andreina; Piccolella, Simona; Pepi, Federico; Patsilinakos, Alexandros; Ragno, Rino; Garzoli, Stefania; Giacomello, Pierluigi

    2012-11-01

    2-Furaldehyde (2-FA), also known as furfural or 2-furancarboxaldehyde, is an heterocyclic aldehyde that can be obtained from the thermal dehydration of pentose monosaccharides. This molecule can be considered as an important sustainable intermediate for the preparation of a great variety of chemicals, pharmaceuticals and furan-based polymers. Despite the great importance of this molecule, its gas-phase basicity (GB) has never been measured. In this work, the GB of 2-FA was determined by the extended Cooks's kinetic method from electrospray ionization triple quadrupole tandem mass spectrometric experiments along with theoretical calculations. As expected, computational results identify the aldehydic oxygen atom of 2-FA as the preferred protonation site. The geometries of O-O-cis and O-O-trans 2-FA and of their six different protomers were calculated at the B3LYP/aug-TZV(d,p) level of theory; proton affinity (PA) values were also calculated at the G3(MP2, CCSD(T)) level of theory. The experimental PA was estimated to be 847.9 ± 3.8 kJ mol(-1), the protonation entropy 115.1 ± 5.03 J mol(-1) K(-1) and the GB 813.6 ± 4.08 kJ mol(-1) at 298 K. From the PA value, a ΔH°(f) of 533.0 ± 12.4 kJ mol(-1) for protonated 2-FA was derived. PMID:23147827

  5. Microwave-assisted hydrothermal synthesis of Cu/Cu2O hollow spheres with enhanced photocatalytic and gas sensing activities at room temperature.

    PubMed

    Zou, Xinwei; Fan, Huiqing; Tian, Yuming; Zhang, Mingang; Yan, Xiaoyan

    2015-05-01

    Cu/Cu2O nano-heterostructure hollow spheres with a submicron diameter (200-500 nm) were prepared by a microwave-assisted hydrothermal method using Cu(OAc)2·H2O, PVP and ascorbic acid solution as the precursors. The morphology of the products could evolve with the hydrothermal time from solid spheres to thick-shell hollow spheres, then to thin-shell hollow spheres, and finally to nanoparticles. Moreover, the content of Cu in the products could be controlled by adjusting the hydrothermal time. The spontaneous forming of the hollow structure spheres was found to result from the Ostwald ripening effect during the low temperature (100 °C) hydrothermal reaction process. The photocatalytic degradation activities on MO under visible-light irradiation and the gas sensing activities toward the oxidizing NO2 gas of different Cu/Cu2O nano-heterostructure hollow spheres were investigated. As a result, the Cu/Cu2O nano-heterostructure hollow spheres obtained at the hydrothermal time of 30 min, with a rough/porous thin-shell structure and a Cu content of about 10.5 wt%, exhibited the best photocatalytic and gas sensing performances compared with others. PMID:25820327

  6. Hydrocarbon radical thermochemistry: Gas-phase ion chemistry techniques

    SciTech Connect

    Ervin, Kent M.

    2014-03-21

    Final Scientific/Technical Report for the project "Hydrocarbon Radical Thermochemistry: Gas-Phase Ion Chemistry Techniques." The objective of this project is to exploit gas-phase ion chemistry techniques for determination of thermochemical values for neutral hydrocarbon radicals of importance in combustion kinetics.

  7. Pressure Dependence of Gas-Phase Reaction Rates

    ERIC Educational Resources Information Center

    De Persis, Stephanie; Dollet, Alain; Teyssandier, Francis

    2004-01-01

    It is presented that only simple concepts, mainly taken from activated-complex or transition-state theory, are required to explain and analytically describe the influence of pressure on gas-phase reaction kinetics. The simplest kind of elementary gas-phase reaction is a unimolecular decomposition reaction.

  8. Gas-phase protonation thermochemistry of arginine.

    PubMed

    Bouchoux, Guy; Desaphy, Sylvain; Bourcier, Sophie; Malosse, Christian; Bimbong, Rosa Ngo Biboum

    2008-03-20

    The gas-phase basicity (GB), proton affinity (PA), and protonation entropy (DeltapS degrees (M)=S degrees (MH+)-S degrees (M)) of arginine (Arg) have been experimentally determined by the extended kinetic method using an electrospray ionization quadrupole time-of-flight (ESI-Q-TOF) mass spectrometer. This method provides GB(Arg)=1004.3+/-2.2 (4.9) kJ.mol(-1) (indicated errors are standard deviations, and in parentheses, 95% confidence limits are given). Consideration of previous experimental data using a fast atom bombardment ionization tandem sector mass spectrometer slightly modifies these estimates since GB(Arg)=1005.9+/-3.1 (6.6) kJ.mol(-1). Lower limits of the proton affinity, PA(Arg)=1046+/-4 (7) kJ.mol(-1), and of the "protonation entropy", DeltapS degrees (Arg)=S degrees (ArgH+)-S degrees (Arg)=-27+/-7 (15) J.mol(-1).K(-1), are also provided by the experiments. Theoretical calculations conducted at the B3LYP/6-311+G(3df,2p)//B3LYP/6-31+G(d,p) level, including 298 K enthalpy correction, predict a proton affinity value of ca. 1053 kJ.mol-1 after consideration of isodesmic proton-transfer reactions with guanidine as the reference base. Computations including explicit treatment of hindered rotations and mixing of conformers confirm that a noticeable entropy loss does occur upon protonation, which leads to a theoretical DeltapS degrees (Arg) term of ca. -45 J.mol(-1).K(-1). The following evaluated thermochemical parameter values are proposed: GB(Arg)=1005+/-3 kJ.mol(-1); PA(Arg)=1051+/-5 kJ.mol(-1), and DeltapS degrees (Arg)=-45+/-12 J.mol(-1).K(-1). PMID:18288831

  9. Gas holdup in three-phase immobilized cell bioreactors

    SciTech Connect

    Bajpai, R.; Thompson, J.E.; Davison, B.

    1989-01-01

    A number of studies in the published literature deal with gas holdup in three-phase reactors. However, very few address the cases in which the solid density approaches that of the liquid phases and where low gas velocities are involved. These conditions are commonly encountered in immobilized-cell bubble columns and in fluidized-bed bioreactors. This paper reports the effect of gas and liquid velocity upon gas holdup and bed expansion in fluidized-bed bioreactors. For liquid-fluidization of low-density alginate beads in the absence of gas, the terminal sedimentation velocity (v/sub T/), of the particles is a constant and expansion of the bed follows Richardson and Zaki's correlation. In the presence of gas, however, the apparent terminal sedimentation velocity value is affected by the velocity of the gas and liquid phases. For gas velocities above a minimum value, the calculated value of v/sub T/ depends upon liquid velocity only and a constant bed expansion was observed for a range of gas and liquid flow rates. For the gas-liquid interactions, a modified drift-flux model was found to be valid. For superficial gas velocities between 5 and 17 cm/min, the modified drift-flux velocity was observed to be a function of gas velocity suggesting the prevalence of a coalescence regime. 21 refs., 4 figs., 1 tab.

  10. Comparison of liquid-phase and gas-phase pure thermal cracking on n-hexadecane

    SciTech Connect

    Wu, G.; Katsumura, Yosuke; Matsuura, Chihiro; Ishigure, Kenkichi; Kubo, Junichi

    1996-12-01

    Thermal cracking of n-hexadecane in the mild temperature (330--375 C) range has been investigated in liquid and gas phases. The kinetic data of liquid-phase cracking are shown to be very similar to those of gas-phase cracking. However, the pattern and distribution of the products are greatly phase dependent. In liquid-phase cracking, there is an equimolar distribution of n-alkane and 1-alkene products in the C{sub 3}--C{sub 13} range at low conversion; when the conversion is increased, more alkanes than alkenes are produced. To the contrary, more alkenes than alkanes are always determined in products from gas-phase cracking. Liquid-phase cracking gives a low selectivity of gas products and a high selectivity of addition compounds (C{sub 18}--C{sub 30}), whereas gas-phase cracking produces a large amount of gas products and no addition compounds. The phase dependence of products can be interpreted in terms of a low concentration of hexadecane, under which {beta}-scission occurs more preferentially than in liquid phase. Reaction mechanisms are suggested based on the product analysis to account for cracking behaviors of liquid-phase and gas-phase cracking.

  11. Gas-Liquid Flows and Phase Separation

    NASA Technical Reports Server (NTRS)

    McQuillen, John

    2004-01-01

    Common issues for space system designers include:Ability to Verify Performance in Normal Gravity prior to Deployment; System Stability; Phase Accumulation & Shedding; Phase Separation; Flow Distribution through Tees & Manifolds Boiling Crisis; Heat Transfer Coefficient; and Pressure Drop.The report concludes:Guidance similar to "A design that operates in a single phase is less complex than a design that has two-phase flow" is not always true considering the amount of effort spent on pressurizing, subcooling and phase separators to ensure single phase operation. While there is still much to learn about two-phase flow in reduced gravity, we have a good start. Focus now needs to be directed more towards system level problems .

  12. Mixed Stationary Liquid Phases for Gas-Liquid Chromatography.

    ERIC Educational Resources Information Center

    Koury, Albert M.; Parcher, Jon F.

    1979-01-01

    Describes a laboratory technique for use in an undergraduate instrumental analysis course that, using the interpretation of window diagrams, prepares a mixed liquid phase column for gas-liquid chromatography. A detailed procedure is provided. (BT)

  13. High resolution ion mobility measurements for gas phase proteins: correlation between solution phase and gas phase conformations

    NASA Astrophysics Data System (ADS)

    Hudgins, Robert R.; Woenckhaus, Jürgen; Jarrold, Martin F.

    1997-11-01

    Our high resolution ion mobility apparatus has been modified by attaching an electrospray source to perform measurements for biological molecules. While the greater resolving power permits the resolution of more conformations for BPTI and cytochrome c, the resolved features are generally much broader than expected for a single rigid conformation. A major advantage of the new experimental configuration is the much gentler introduction of ions into the drift tube, so that the observed gas phase conformations appear to more closely reflect those present in solution. For example, it is possible to distinguish between the native state of cytochrome c and the methanol-denatured form on the basis of the ion mobility measurements; the mass spectra alone are not sensitive enough to detect this change. Thus this approach may provide a quick and sensitive tool for probing the solution phase conformations of biological molecules.

  14. Electron spectrometer for gas-phase spectroscopy

    SciTech Connect

    Bozek, J.D.; Schlachter, A.S.

    1997-04-01

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

  15. Photocatalytic degradation of bisphenol A using an integrated system of a new gas-liquid-solid circulating fluidized bed reactor and micrometer Gd-doped TiO2 particles.

    PubMed

    Cheng, Zhiliang; Quan, Xuejun; Xiang, Jinxin; Huang, Yuming; Xu, Yunlan

    2012-01-01

    A new gas-liquid-solid circulating fluidized bed photocatalytic reactor (GLSCFBPR) with internally placed multi-layered UV lamps was developed. Micrometer Gd-TiO2 particles and commercial nanometer P25-TiO2 were chosen as the photocatalysts, and the hazardous substance bisphenol A (BPA) was chosen as the model pollutant to investigate the performance of this new photocatalytic system. The results showed that the photocatalytic degradation efficiency of the micrometer Gd-TiO2 particles was similar to that of the nanometer P-25 particles at their respective optimum dosage but the former could be easily separated out by gravity. After investigating the effects of process parameters on the photocatalytic BPA degradation, the response surface method (RSM) was further used for process optimization. The interactions among process parameters, i.e., TiO2 concentration, superficial gas velocity and superficial liquid velocity were discovered and a related analysis was carried out to explore the underlying mechanism. A quadratic mathematic model was established and performed satisfactorily when used for prediction. The optimum conditions for this new process were as follows: TiO2 concentration 4.5 g/L, superficial gas velocity 7.83 x 10(-3) m/sec and superficial liquid velocity 8.65 x 10(-3) m/sec. PMID:23513453

  16. Synthesis and photocatalytic activity of N-doped TiO2 produced in a solid phase reaction

    NASA Astrophysics Data System (ADS)

    Xin, Gang; Pan, Hongfei; Chen, Dan; Zhang, Zhihua; Wen, Bin

    2013-02-01

    N-doped TiO2 was synthesized by calcining a mixture of titanic acid and graphitic carbon nitride (g-C3N4) at temperatures above 500 °C. The final samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS), and UV-vis diffuse reflectance spectra. The photocatalytic activity of N-doped TiO2 was studied by assessing the degradation of methylene blue in an aqueous solution, under visible light and UV light irradiation. It was found that the N-doped TiO2 displayed higher photocatalytic activity than pure TiO2, under both visible and UV light.

  17. Phase-Dependent Photocatalytic Ability of TiO2: A First-Principles Study

    SciTech Connect

    Pan, Hui; Gu, Baohua; Zhang, Zhenyu

    2009-01-01

    Abstract: The electronic properties of defected TiO2 were investigated using the first-principles calculations based on density functional theory and generalized gradient approximation. Three typical defects, oxygen vacancy, titanium interstitial, and titanium vacancy, were considered in three TiO2 polymorphs, anatase, rutile, and brookite, respectively. Our calculations demonstrated that defect band is formed by removing oxygen atom from or inserting interstitial Ti atom into the TiO2 lattice, which is responsible for the improvement of photocatalytic ability due to the enhanced visible-light absorption. Our calculations further revealed that the defect formation energy increases as following brookite, anatase, and rutile, indicating that defects are easy to be created in brookite TiO2. The relatively high defect density and wide defect band contribute to the better photocatalytic performance of brookite TiO2 in visible light.

  18. Gas phase acetaldehyde production in a continuous bioreactor

    SciTech Connect

    Hwang, Soon Ook . Dept. of Chemical Engineering); Trantolo, D.J. . Center for Biotechnology Engineering); Wise, D.L. . Dept. of Chemical Engineering Northeastern Univ., Boston, MA . Center for Biotechnology Engineering)

    1993-08-20

    The gas phase continuous production of acetaldehyde was studied with particular emphasis on the development of biocatalyst (alcohol oxidase on solid phase support materials) for a fixed bed reactor. Based on the experimental results in a batch bioreactor, the biocatalysts were prepared by immobilization of alcohol oxidase on Amberlite IRA-400, packed into a column, and the continuous acetaldehyde production in the gas phase by alcohol oxidase was performed. The effects of the reaction temperature, flow rates of gaseous stream, and ethanol vapor concentration on the performance of the continuous bioreactor were investigated.

  19. Gas-phase diffusion in porous media: Comparison of models

    SciTech Connect

    Webb, S.W.

    1998-09-01

    Two models are commonly used to analyze gas-phase diffusion in porous media in the presence of advection, the Advective-Dispersive Model (ADM) and the Dusty-gas Model (DGM). The ADM, which is used in TOUGH2, is based on a simple linear addition of advection calculated by Darcy`s law and ordinary diffusion using Fick`s law with a porosity-tortuosity-gas saturation multiplier to account for the porous medium. Another approach for gas-phase transport in porous media is the Dusty-Gas Model. This model applies the kinetic theory of gases to the gaseous components and the porous media (or dust) to combine transport due to diffusion and advection that includes porous medium effects. The two approaches are compared in this paper.

  20. Para-Hydrogen-Enhanced Gas-Phase Magnetic Resonance Imaging

    SciTech Connect

    Bouchard, Louis-S.; Kovtunov, Kirill V.; Burt, Scott R.; Anwar,M. Sabieh; Koptyug, Igor V.; Sagdeev, Renad Z.; Pines, Alexander

    2007-02-23

    Herein, we demonstrate magnetic resonance imaging (MRI) inthe gas phase using para-hydrogen (p-H2)-induced polarization. A reactantmixture of H2 enriched in the paraspin state and propylene gas is flowedthrough a reactor cell containing a heterogenized catalyst, Wilkinson'scatalyst immobilized on modified silica gel. The hydrogenation product,propane gas, is transferred to the NMR magnet and is spin-polarized as aresult of the ALTADENA (adiabatic longitudinal transport and dissociationengenders net alignment) effect. A polarization enhancement factor of 300relative to thermally polarized gas was observed in 1D1H NMR spectra.Enhancement was also evident in the magnetic resonance images. This isthe first demonstration of imaging a hyperpolarized gaseous productformed in a hydrogenation reaction catalyzed by a supported catalyst.This result may lead to several important applications, includingflow-through porous materials, gas-phase reaction kinetics and adsorptionstudies, and MRI in low fields, all using catalyst-free polarizedfluids.

  1. Constant volume gas cell optical phase-shifter

    DOEpatents

    Phillion, Donald W.

    2002-01-01

    A constant volume gas cell optical phase-shifter, particularly applicable for phase-shifting interferometry, contains a sealed volume of atmospheric gas at a pressure somewhat different than atmospheric. An optical window is present at each end of the cell, and as the length of the cell is changed, the optical path length of a laser beam traversing the cell changes. The cell comprises movable coaxial tubes with seals and a volume equalizing opening. Because the cell is constant volume, the pressure, temperature, and density of the contained gas do not change as the cell changes length. This produces an exactly linear relationship between the change in the length of the gas cell and the change in optical phase of the laser beam traversing it. Because the refractive index difference between the gas inside and the atmosphere outside is very much the same, a large motion must be made to change the optical phase by the small fraction of a wavelength that is required by phase-shifting interferometry for its phase step. This motion can be made to great fractional accuracy.

  2. Construction of α-β Phase Junction on Bi4V2O11 via Electrospinning Retardation Effect and Its Promoted Photocatalytic Performance.

    PubMed

    Lv, Chade; Chen, Gang; Sun, Jingxue; Zhou, Yansong

    2016-05-16

    The creation of a phase junction structure in photocatalysts is a wise approach to promote photocatalytic performance, as phase junctions possess the potential to inhibit the recombination of photoinduced charge carriers. Here, Bi4V2O11 nanofibers with an α-β phase junction are fabricated via electrospinning with subsequent calcination. Electrospinning offers the opportunity to keep α-Bi4V2O11 from transforming into β-Bi4V2O11 completely due to an electrospinning retardation effect, leading to the formation of an α-β Bi4V2O11 phase junction. Furthermore, the α-β Bi4V2O11 phase junction realizes a well-established type-II band alignment. Photoelectrochemical measurements and photoluminescence spectroscopic investigations demonstrate that the phase junction structure has a significant impact on the separation and transfer of photogenerated electrons and holes. Thus, the α-β phase junction on Bi4V2O11 holds the key to achieving promoted efficiency in the photocatalysis process. PMID:27135691

  3. Oscillatory burning of solid propellants including gas phase time lag.

    NASA Technical Reports Server (NTRS)

    T'Ien, J. S.

    1972-01-01

    An analysis has been performed for oscillatory burning of solid propellants including gas phase time lag. The gaseous flame is assumed to be premixed and laminar with a one-step overall chemical reaction. The propellant is assumed to decompose according to the Arrenhius Law, with no condensed phase reaction. With this model, strong gas phase resonance has been found in certain cases at the characteristic gas-phase frequencies, but the peaking of the acoustic admittance is in the direction favoring the damping of pressure waves. At still higher frequencies, moderate wave-amplifying ability was found. The limit of low frequency response obtained previously by Denison and Baum was recovered, and the limitations of the quasi-steady theory were investigated.

  4. Phase Transition of Methane Gas Hydrate and Response of Marine Gas Hydrate Systems to Environmental Changes

    NASA Astrophysics Data System (ADS)

    Xu, W.

    2003-12-01

    Gas hydrates, which contain mostly methane as the gas component in marine sediment, are stable under relatively high pressure and low temperature conditions such as those found along continental margins and permafrost regions. Its stability is mostly controlled by in-situ pressure, temperature and salinity of pore fluid. Environmentally introduced changes in pressure and temperature can affect the stability of gas hydrate in marine sediment. While certain changes may enhance the process of gas hydrate formation, we are much more interested in the resultant dissociation processes, which may contribute to sub-marine slope instability, seafloor sediment failure, formation of mud volcanoes and pock marks, potential vulnerability of engineering structures, and the risk to drilling and production. We have been developing models to quantify phase transition processes of marine gas hydrates and to investigate the response of marine gas hydrate systems to environmental changes. Methane gas hydrate system is considered as a three-component (water, methane, salt) four-phase (liquid, gas, hydrate, halite) system. Pressure, temperature and salinity of pore fluid constrain the stability of gas hydrate and affect phase transition processes via their effects on methane solubility and fluid density and enthalpy. Compared to the great quantity of studies on its stability in the literature, in-depth research on phase transition of gas hydrate is surprisingly much less. A method, which employs pressure, enthalpy, salinity and methane content as independent variables, is developed to calculate phase transition processes of the three-component four-phase system. Temperature, an intensive thermodynamic parameter, is found not sufficient in describing phase transition of gas hydrate. The extensive thermodynamic parameter enthalpy, on the other hand, is found to be sufficient both in calculation of the phase transition processes and in modeling marine gas hydrate systems. Processes

  5. Tm-doped TiO2 and Tm2Ti2O7 pyrochlore nanoparticles: enhancing the photocatalytic activity of rutile with a pyrochlore phase

    PubMed Central

    De los Santos, Desiré M; Aguilar, Teresa; Sánchez-Coronilla, Antonio; Fernández-Lorenzo, Concha; Alcántara, Rodrigo; Piñero, Jose Carlos; Blanco, Ginesa; Martín-Calleja, Joaquín

    2015-01-01

    Summary Tm-doped TiO2 nanoparticles were synthesized using a water-controlled hydrolysis reaction. Analysis was performed in order to determine the influence of the dopant concentration and annealing temperature on the phase, crystallinity, and electronic and optical properties of the resulting material. Various characterization techniques were utilized such as X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and UV–vis spectroscopy. For the samples annealed at 773 and 973 K, anatase phase TiO2 was obtained, predominantly internally doped with Tm3+. ICP–AES showed that a doping concentration of up to 5.8 atom % was obtained without reducing the crystallinity of the samples. The presence of Tm3+ was confirmed by X-ray photoelectron spectroscopy and UV–vis spectroscopy: the incorporation of Tm3+ was confirmed by the generation of new absorption bands that could be assigned to Tm3+ transitions. Furthermore, when the samples were annealed at 1173 K, a pyrochlore phase (Tm2Ti2O7) mixed with TiO2 was obtained with a predominant rutile phase. The photodegradation of methylene blue showed that this pyrochlore phase enhanced the photocatalytic activity of the rutile phase. PMID:25821701

  6. Collision-induced gas phase dissociation rates

    NASA Technical Reports Server (NTRS)

    Hansen, C. Frederick

    1990-01-01

    The Landau-Zener theory of reactive cross sections was applied to diatomic molecules dissociating from a ladder of vibrational states. The result predicts a dissociation rate that is quite well duplicated by an Arrhenius function having a preexponential temperature dependence of about T(sub -1/2), at least for inert collision partners. This relation fits experimental data reasonably well. The theory is then used to calculate the effect of vibrational nonequilibrium on dissociation rate. For Morse oscillators, the results are about the same as given by Hammerling, Kivel, and Teare in their analytic approximation for harmonic oscillators, though at very high temperature a correction for the partition function limit is included. The empirical correction for vibration nonequilibrium proposed by Park, which is a convenient algorithm for CFD calculations, is modified to prevent a drastic underestimation of dissociation rates that occurs with this method when vibrational temperature is much smaller than the kinetic temperature of the gas.

  7. Capillary gas chromatography with two new moderately high temperature phases.

    NASA Technical Reports Server (NTRS)

    Pollock, G. E.

    1972-01-01

    Gas chromatography test results are presented for two new moderately high-temperature phases of Dexsil 400-GC with free hydroxyl end groups (uncapped) and with end groups covered by trimethyl silyl groups (capped). The two Dexsil 400-GC phases were tested for their ability to resolve N-TFA-DL-(+)-2-butyl esters and n-butyl esters, as well as fatty acid methyl esters and hydrocarbon standards. Generally the more polar uncapped phase was superior to the capped phase in all separation comparisons, except for the hydrocarbons.

  8. Freeze drying for gas chromatography stationary phase deposition

    DOEpatents

    Sylwester, Alan P.

    2007-01-02

    The present disclosure relates to methods for deposition of gas chromatography (GC) stationary phases into chromatography columns, for example gas chromatography columns. A chromatographic medium is dissolved or suspended in a solvent to form a composition. The composition may be inserted into a chromatographic column. Alternatively, portions of the chromatographic column may be exposed or filled with the composition. The composition is permitted to solidify, and at least a portion of the solvent is removed by vacuum sublimation.

  9. Negative ion gas-phase chemistry of arenes.

    PubMed

    Danikiewicz, Witold; Zimnicka, Magdalena

    2016-01-01

    Reactions of aromatic and heteroaromatic compounds involving anions are of great importance in organic synthesis. Some of these reactions have been studied in the gas phase and are occasionally mentioned in reviews devoted to gas-phase negative ion chemistry, but no reviews exist that collect all existing information about these reactions. This work is intended to fill this gap. In the first part of this review, methods for generating arene anions in the gas phase and studying their physicochemical properties and fragmentation reactions are presented. The main topics in this part are as follows: processes in which gas-phase arene anions are formed, measurements and calculations of the proton affinities of arene anions, proton exchange reactions, and fragmentation processes of substituted arene anions, especially phenide ions. The second part is devoted to gas-phase reactions of arene anions. The most important of these are reactions with electrophiles such as carbonyl compounds and α,β-unsaturated carbonyl and related compounds (Michael acceptors). Other reactions including oxidation of arene anions and halogenophilic reactions are also presented. In the last part of the review, reactions of electrophilic arenes with nucleophiles are discussed. The best known of these is the aromatic nucleophilic substitution (SN Ar) reaction; however, other processes that lead to the substitution of a hydrogen atom in the aromatic ring are also very important. Aromatic substrates in these reactions are usually but not always nitroarenes bearing other substituents in the ring. The first step in these reactions is the formation of an anionic σ-adduct, which, depending on the substituents in the aromatic ring and the structure of the attacking nucleophile, is either an intermediate or a transition state in the reaction path. In the present review, we attempted to collect the results of both experimental and computational studies of the aforementioned reactions conducted since the

  10. Analysis of the gas phase reactivity of chlorosilanes.

    PubMed

    Ravasio, Stefano; Masi, Maurizio; Cavallotti, Carlo

    2013-06-27

    Trichlorosilane is the most used precursor to deposit silicon for photovoltaic applications. Despite of this, its gas phase and surface kinetics have not yet been completely understood. In the present work, it is reported a systematic investigation aimed at determining what is the dominant gas phase chemistry active during the chemical vapor deposition of Si from trichlorosilane. The gas phase mechanism was developed calculating the rate constant of each reaction using conventional transition state theory in the rigid rotor-harmonic oscillator approximation. Torsional vibrations were described using a hindered rotor model. Structures and vibrational frequencies of reactants and transition states were determined at the B3LYP/6-31+G(d,p) level, while potential energy surfaces and activation energies were computed at the CCSD(T) level using aug-cc-pVDZ and aug-cc-pVTZ basis sets extrapolating to the complete basis set limit. As gas phase and surface reactivities are mutually interlinked, simulations were performed using a microkinetic surface mechanism. It was found that the gas phase reactivity follows two different routes. The disilane mechanism, in which the formation of disilanes as reaction intermediates favors the conversion between the most stable monosilane species, and the radical pathway, initiated by the decomposition of Si2HCl5 and followed by a series of fast propagation reactions. Though both mechanisms are active during deposition, the simulations revealed that above a certain temperature and conversion threshold the radical mechanism provides a faster route for the conversion of SiHCl3 into SiCl4, a reaction that favors the overall Si deposition process as it is associated with the consumption of HCl, a fast etchant of Si. Also, this study shows that the formation of disilanes as reactant intermediates promotes significantly the gas phase reactivity, as they contribute both to the initiation of radical chain mechanisms and provide a catalytic route for

  11. Gas purification in the dense phase at the CATS terminal

    SciTech Connect

    Openshaw, P.J.; Carnell, P.J.H.; Rhodes, E.F.

    1999-07-01

    The purification and transportation of natural gas at very high pressures can help to minimize the capital cost of pipelines and processing equipment. However, complex mixtures of hydrocarbons undergo unusual phase changes, such as retrograde condensation, as the temperature and pressure are altered. The Central Area Transmission System (CATS) is a joint venture of Amoci, BG, Amerada Hess, Phillips, Agip and Fina operated by Amoco on behalf of the owners. The design of the CATS terminal has provided an interesting processing challenge. The terminal receives a total of 1.6 Bscf/d of rich gas from a number of offshore fields. All are relatively sweet but the small amounts of H{sub 2}S and Hg are removed. Fixed bed technology was selected as the most economic purification process, while minimizing hydrocarbon loss and operator involvement. Conventionally, the raw gas would be split into the different hydrocarbon fractions and each would be processed separately. This would require the installation of a large number of reactors. A more elegant solution is to treat the gas on arrival at the terminal in the dense phase. This option raised questions around whether a fixed bed would be prone to fouling, could the pressure drop be kept low enough to avoid phase separation and would inadvertent wetting by condensation cause problems. Details are given of the test work carried out to prove the viability of using fixed bed technology for dense phase gas processing, the eventual design adopted and the performance over the first year of service.

  12. Gas phase radiative effects in diffusion flames

    NASA Astrophysics Data System (ADS)

    Bedir, Hasan

    Several radiation models are evaluated for a stagnation point diffusion flame of a solid fuel in terms of accuracy and computational time. Narrowband, wideband, spectral line weighted sum of gray gases (SLWSGG), and gray gas models are included in the comparison. Radiative heat flux predictions by the nongray narrowband, wideband, and SLWSGG models are found to be in good agreement with each other, whereas the gray gas models are found to be inaccurate. The narrowband model, the most complex among the models evaluated, is then applied first to a solid fuel and second to a pure gaseous diffusion flame. A polymethylmethacrylate (PMMA) diffusion flame in a stagnation point geometry is solved with the narrowband model with COsb2, Hsb2O, and MMA vapor included in participating species. A detailed account of the emission and absorption from these species as well as the radiative heat fluxes are given as a function of the stretch rate. It is found that at low stretch rate the importance of radiation is increased due to an increase in the optical thickness, and a decrease in the conductive heat flux. Results show that COsb2 is the biggest emitter and absorber in the flame, MMA vapor is the second and Hsb2O is the least important. A pure gaseous flame in an opposed jet configuration is solved with the narrowband radiation model with CO as the fuel, and Osb2 as the oxidizer. Detailed. chemical kinetics and transport are incorporated into the combustion model with the use of the CHEMKIN and TRANSPORT software packages. The governing equations are solved with a modified version of the OPPDIF code. Dry and wet CO flames as well as COsb2 dilution are studied. Comparison of the results with and without the consideration of radiation reveals that the radiation is important for the whole flammable range of dry CO flames and for the low stretch rates of wet flames. Without the consideration of radiation the temperature and the species mole fractions (especially of minor species

  13. Calculation of two-phase flow in gas turbine combustors

    SciTech Connect

    Tolpadi, A.K.

    1995-10-01

    A method is presented for computing steady two-phase turbulent combusting flow in a gas turbine combustor. The gas phase equations are solved in an Eulerian frame of reference. The two-phase calculations are performed by using a liquid droplet spray combustion a model and treating the motion of the evaporating fuel droplets in a Lagrangian frame of reference. The numerical algorithm employs nonorthogonal curvilinear coordinates, a multigrid iterative solution procedure, the standard k-{epsilon} turbulence model, and a combustion model comprising an assumed shape probability density function and the conserved scalar formulation. The trajectory computation of the fuel provides the source terms for all the gas phase equations. This two-phase model was applied to a real piece of combustion hardware in the form of a modern GE/SNECMA single annular CFM56 turbofan engine combustor. For the purposes of comparison, calculations were also performed by treating the fuel as a single gaseous phase. The effect on the solution of two extreme situations of the fuel as a gas and initially as a liquid was examined. The distribution of the velocity field and the conserved scalar within the combustor, as well as the distribution of the temperature field in the reaction zone and in the exhaust, were all predicted with the combustor operating both at high-power and low-power (ground idle) conditions. The calculated exit gas temperature was compared with test rig measurements. Under both low and high-power conditions, the temperature appeared to show an improved agreement with the measured data when the calculations were performed with the spray model as compared to a single-phase calculation.

  14. New anatase-type Til-2xNbxAlxO2 solid solution nanoparticles: direct formation, phase stability, and photocatalytic performance.

    PubMed

    Hirano, Masanori; Ito, Takaharu

    2006-12-01

    New anatase-type titania solid solutions co-doped with niobium and aluminum (Til-2xNbxAIlxO2 (X = 0 -0.20)) were synthesized as nanoparticles from precursor solutions of TiOSO4, NbCl5, and Al(NO3)3 under mild hydrothermal conditions at 180 degrees C for 5 h using the hydrolysis of urea. The lattice parameters a0 and c0 of anatase slightly and gradually increased, when the content of niobium and aluminum increased from X = 0 to 0.20. The crystallite size of anatase increased from 12 to 28 nm with increasing the value of X from 0 to 0.20. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution in the dark or under UV-light irradiation. The adsorptivity of TiO2 was improved by the formation of anatase-type Til-2xNbxAlxO2 solid solutions. The photocatalytic activity of anatase-type Til-2xNbxAlxO2 solid solutions was superior to that of commercially available anatase-type pure TiO2 (ST-01) and anatase-type pure TiO2 hydrothermally prepared. The new anatase phase of Til-2xNbxAlxO2 (X = 0-0.20) solid solutions existed stably up to 850 0C during heat treatment in air. In comparison with hydrothermal pure TiO2, the starting temperature of anatase-to-rutile phase transformation was delayed by the formation of Ti1-2xNbxAlxO, (X = 0-0.20) solid solutions, although its completing temperature was accelerated. PMID:17256336

  15. Parameters Influencing the Photocatalytic Activity of Suspension-Sprayed TiO2 Coatings

    NASA Astrophysics Data System (ADS)

    Toma, Filofteia-Laura; Berger, Lutz-Michael; Shakhverdova, Irina; Leupolt, Beate; Potthoff, Annegret; Oelschlägel, Kathrin; Meissner, Tobias; Gomez, José Antonio Ibáñez; de Miguel, Yolanda

    2014-10-01

    Photocatalytic properties of titania have been studied very intensively for a variety of applications, including air and water purification. In order to clarify the influence of the phase composition and other parameters, thermal spraying with suspensions was applied to produce photocatalytically active titania coatings starting from two commercially available anatase and rutile submicron powders. Aqueous suspensions containing 40% solids by weight were sprayed with an HVOF process using ethylene as the fuel gas. The spray parameters were chosen in order to produce mechanically stable coatings and to preserve a high content of the initial crystalline phases of the powders. The coating microstructures, phase compositions, and surface properties were characterized. The photocatalytic performance was evaluated by degradation of the pink dye Rhodamine B (RB) using two techniques: degradation of an aqueous solution of RB and discoloration of impregnated RB. All the coatings exhibited photocatalytic activity to varying degrees, depending on the phase composition as well as other factors, namely, the coating microstructure, surface morphology, surface hydroxylation, light absorption, and interaction with the pollutant.

  16. LOW COST IMAGER FOR POLLUTANT GAS LEAK DETECTION - PHASE II

    EPA Science Inventory

    An inexpensive imaging Instrument to quickly locate leaks of methane and other greenhouse and VOC gases would reduce the cost and effort expended by industry to comply with EPA regulations. In Phase I, of this WBIR program, a new gas leak visualization camera was demonstrated...

  17. Statistical and Microscopic Approach to Gas Phase Chemical Kinetics.

    ERIC Educational Resources Information Center

    Perez, J. M.; Quereda, R.

    1983-01-01

    Describes advanced undergraduate laboratory exercise examining the dependence of the rate constants and the instantaneous concentrations with the nature and energy content in a gas-phase complex reaction. Computer program (with instructions and computation flow charts) used with the exercise is available from the author. (Author/JN)

  18. Apparatus for the premixed gas phase combustion of liquid fuels

    SciTech Connect

    Roffe, G.A.; Trucco, H.A.

    1981-04-21

    This invention relates to improvements in the art of liquid fuel combustion and, more particularly, concerns a method and apparatus for the controlled gasification of liquid fuels, the thorough premixing of the then gasified fuel with air and the subsequent gas-phase combustion of the mixture to produce a flame substantially free of soot, carbon monoxide, nitric oxide and unburned fuel.

  19. INVESTIGATION OF GAS-PHASE OZONE AS A POTENTIAL BIOCIDE

    EPA Science Inventory

    The paper presents data on the effect of ozone on both vegetative and spore-forming fungi as well as on spore-forming bacteria. (NOTE: Despite the wide use of ozone generators in indoor air cleaning, there is little research data on ozone's biocidal activity in the gas phase.) Dr...

  20. Can the ordinary chondrites have condensed from a gas phase

    NASA Technical Reports Server (NTRS)

    Herndon, J. M.; Suess, H. E.

    1977-01-01

    The conditions under which ordinary chondrites containing iron in three different chemical states can form in thermodynamic equilibrium with a gas phase are calculated. Hydrogen depletion factors of 100-1000 are obtained and the formation of liquid condensates from residual gases occurs at pressures (prior to hydrogen depletion) of roughly equal to or greater than 1 atm.

  1. Ion-Molecule Reactions in Gas Phase Radiation Chemistry.

    ERIC Educational Resources Information Center

    Willis, Clive

    1981-01-01

    Discusses some aspects of the radiation chemistry of gases, focusing on the ion-molecule and charge neutralization reactions which set study of the gas phase apart. Uses three examples that illustrate radiolysis, describing the radiolysis of (1) oxygen, (2) carbon dioxide, and (3) acetylene. (CS)

  2. Novel stationary phases based on asphaltenes for gas chromatography.

    PubMed

    Boczkaj, Grzegorz; Momotko, Malwina; Chruszczyk, Dorota; Przyjazny, Andrzej; Kamiński, Marian

    2016-07-01

    We present the results of investigations on the possibility of the application of the asphaltene fraction isolated from the oxidized residue from vacuum distillation of crude oil as a stationary phase for gas chromatography. The results of the investigation revealed that the asphaltene stationary phases can find use for the separation of a wide range of volatile organic compounds. The experimental values of Rohrschneider/McReynolds constants characterize the asphaltenes as stationary phases of medium polarity and selectivity similar to commercially available phases based on alkyl phthalates. Isolation of asphaltenes from the material obtained under controlled process conditions allows the production of a stationary phase having reproducible sorption properties and chromatographic columns having the same selectivity. Unique selectivity and high thermal stability make asphaltenes attractive as a material for stationary phases for gas chromatography. A low production cost from a readily available raw material (oxidized petroleum bitumens) is an important economic factor in case of application of the asphaltene stationary phases for preparative and process separations. PMID:27144876

  3. Charged supramolecular assemblies of surfactant molecules in gas phase.

    PubMed

    Bongiorno, David; Ceraulo, Leopoldo; Indelicato, Sergio; Turco Liveri, Vincenzo; Indelicato, Serena

    2016-01-01

    The aim of this review is to critically analyze recent literature on charged supramolecular assemblies formed by surfactant molecules in gas phase. Apart our specific interest on this research area, the stimuli to undertake the task arise from the widespread theoretical and applicative benefits emerging from a comprehensive view of this topic. In fact, the study of the formation, stability, and physicochemical peculiarities of non-covalent assemblies of surfactant molecules in gas phase allows to unveil interesting aspects such as the role of attractive, repulsive, and steric intermolecular interactions as driving force of supramolecular organization in absence of interactions with surrounding medium and the size and charge state dependence of aggregate structural and dynamical properties. Other interesting aspects worth to be investigated are joined to the ability of these assemblies to incorporate selected solubilizates molecules as well as to give rise to chemical reactions within a single organized structure. In particular, the incorporation of large molecules such as proteins has been of recent interest with the objective to protect their structure and functionality during the transition from solution to gas phase. Exciting fall-out of the study of gas phase surfactant aggregates includes mass and energy transport in the atmosphere, origin of life and simulation of supramolecular aggregation in the interstellar space. Moreover, supramolecular assemblies of amphiphilic molecules in gas phase could find remarkable applications as atmospheric cleaning agents, nanosolvents and nanoreactors for specialized chemical processes in confined space. Mass spectrometry techniques have proven to be particularly suitable to generate these assemblies and to furnish useful information on their size, size polydispersity, stability, and structural organization. On the other hand molecular dynamics simulations have been very useful to rationalize many experimental findings and to

  4. Gas Phase Reactivity of Carboxylates with N-Hydroxysuccinimide Esters

    NASA Astrophysics Data System (ADS)

    Peng, Zhou; McGee, William M.; Bu, Jiexun; Barefoot, Nathan Z.; McLuckey, Scott A.

    2015-01-01

    N-hydroxysuccinimide (NHS) esters have been used for gas-phase conjugation reactions with peptides at nucleophilic sites, such as primary amines (N-terminus, ɛ-amine of lysine) or guanidines, by forming amide bonds through a nucleophilic attack on the carbonyl carbon. The carboxylate has recently been found to also be a reactive nucleophile capable of initiating a similar nucleophilic attack to form a labile anhydride bond. The fragile bond is easily cleaved, resulting in an oxygen transfer from the carboxylate-containing species to the reagent, nominally observed as a water transfer. This reactivity is shown for both peptides and non-peptidic species. Reagents isotopically labeled with O18 were used to confirm reactivity. This constitutes an example of distinct differences in reactivity of carboxylates between the gas phase, where they are shown to be reactive, and the solution phase, where they are not regarded as reactive with NHS esters.

  5. Liquid-gas phase transition in nuclear matter including strangeness

    SciTech Connect

    Wang, P.; Leinweber, D.B.; Williams, A.G.; Thomas, A.W.

    2004-11-01

    We apply the chiral SU(3) quark mean field model to study the properties of strange hadronic matter at finite temperature. The liquid-gas phase transition is studied as a function of the strangeness fraction. The pressure of the system cannot remain constant during the phase transition, since there are two independent conserved charges (baryon and strangeness number). In a range of temperatures around 15 MeV (precise values depending on the model used) the equation of state exhibits multiple bifurcates. The difference in the strangeness fraction f{sub s} between the liquid and gas phases is small when they coexist. The critical temperature of strange matter turns out to be a nontrivial function of the strangeness fraction.

  6. Gas-phase exposure history derived from material-phase concentration profiles

    NASA Astrophysics Data System (ADS)

    Morrison, G. C.; Little, J. C.; Xu, Y.; Rao, M.; Enke, D.

    Non-reactive gas-phase pollutants such as benzene diffuse into indoor furnishings and leave behind a unique material-phase concentration profile that serves as a record of the past gas-phase indoor concentrations. The inverse problem to be solved is the diffusion equation in a slab such as vinyl flooring. Using knowledge of the present material-phase concentration profile in the slab, we seek to determine the historical material-phase concentration at the surface exposed to indoor air, and hence the historical gas-phase concentration, which can be used directly to determine exposure. The problem as posed has a unique solution that may be solved using a variety of approaches. We use a trained artificial neural network (ANN) to derive solutions for hypothetical exposure scenarios. The ANN results show that it is possible to estimate the intensity and timing of past exposures from the material-phase concentration profile in a building material. The overall method is limited by (1) the resolution of techniques for measuring spatial material-phase concentration profiles, (2) how far back in time we seek to determine exposure and (3) the representational power of the ANN solution. For example, we estimate that this technique can estimate exposure to phenol up to 0.5 y in the past from analyses of vinyl flooring.

  7. Gas phase decontamination of gaseous diffusion process equipment

    SciTech Connect

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

    1994-03-01

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

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

    SciTech Connect

    Munday, E.B.

    1993-12-01

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

  9. Lattice-gas models of phase separation: interfaces, phase transitions, and multiphase flow

    SciTech Connect

    Rothman, D.H. ); Zaleski, S. )

    1994-10-01

    Momentum-conserving lattice gases are simple, discrete, microscopic models of fluids. This review describes their hydrodynamics, with particular attention given to the derivation of macroscopic constitutive equations from microscopic dynamics. Lattice-gas models of phase separation receive special emphasis. The current understanding of phase transitions in these momentum-conserving models is reviewed; included in this discussion is a summary of the dynamical properties of interfaces. Because the phase-separation models are microscopically time irreversible, interesting questions are raised about their relationship to real fluid mixtures. Simulation of certain complex-fluid problems, such as multiphase flow through porous media and the interaction of phase transitions with hydrodynamics, is illustrated.

  10. Gas Phase Chemical Detection with an Integrated Chemical Analysis System

    SciTech Connect

    Baca, Albert G.; Casalnuovo, Stephen A.; Frye-Mason, Gregory C.; Heller, Edwin J.; Hietala, Susan L.; Hietala, Vincent M.; Kottenstette, Richard J.; Lewis, Patrick R.; Manginell, Ronald P.; Matzke, Carloyn M.; Reno, John L.; Sasaki, Darryl Y.; Schubert, W. Kent

    1999-07-08

    Microfabrication technology has been applied to the development of a miniature, multi-channel gas phase chemical laboratory that provides fast response, small size, and enhanced versatility and chemical discrimination. Each analysis channel includes a sample concentrator followed by a gas chromatographic separator and a chemically selective surface acoustic wave detector array to achieve high sensitivity and selectivity. The performance of the components, individually and collectively, is described. The design and performance of novel micromachined acoustic wave devices, with the potential for improved chemical sensitivity, are also described.

  11. Collaborative Advanced Gas Turbine Program: Phase 1. Final report

    SciTech Connect

    Hollenbacher, R.; Kesser, K.; Beishon, D.

    1994-12-01

    The Collaborative Advanced Gas Turbine (CAGT) Program is an advanced gas turbine research and development program whose goal is to accelerate the commercial availability, to within the turn of the century, of high efficiency aeroderivative gas turbines for electric power generating applications. In the first project phase, research was conducted to prove or disprove the research hypothesis that advanced aeroderivative gas turbine systems can provide a promising technology alternative, offering high efficiency and good environmental performance characteristics in modular sizes, for utility applications. This $5 million, Phase 1 research effort reflects the collaborative efforts of a broad and international coalition of industries and organizations, both public and private, that have pooled their resources to assist in this research. Included in this coalition are: electric and gas utilities, the Electric Power Research Institute, the Gas Research Institute and the principal aircraft engine manufacturers. Additionally, the US Department of Energy (DOE) and the California Energy Commission have interacted with the CAGT on both technical and executive levels as observers and sources of funding. The three aircraft engine manufacturer-led research teams participating in this research include: Rolls-Royce, Inc., and Bechtel; the Turbo Power and Marine Division of United Technologies and Fluor Daniel; and General Electric Power Generation, Stewart and Stevenson, and Bechtel. Each team has investigated advanced electric power generating systems based on their high-thrust (60,000 to 100,000 pounds) aircraft engines. The ultimate goal of the CAGT program is that the community of stakeholders in the growing market for natural-gas-fueled, electric power generation can collectively provide the right combination of market-pull and technology-push to substantially accelerate the commercialization of advanced, high efficiency aeroderivative technologies.

  12. Integration of photocatalytic oxidation with air stripping of contaminated aquifers. Report for 1 October 1993--30 June 1997

    SciTech Connect

    Changrani, R.; Raupp, G.B.; Turchi, C.

    1998-12-01

    The global objective of this work was to evaluate the integration of gas-solid ultraviolet (UV) photocatalytic oxidation (PCO) downstream of an air stripper as a technology for cost-effectively treating water pumped from an aquifer contaminated with chlorinated volatile organic compounds (VOCs). Experimental work was performed at the bench-scale in the laboratory during the first phase of the project, and at the pilot-scale in a simulated field-test situation during the second phase.

  13. Chemistry inside molecular containers in the gas phase

    NASA Astrophysics Data System (ADS)

    Lee, Tung-Chun; Kalenius, Elina; Lazar, Alexandra I.; Assaf, Khaleel I.; Kuhnert, Nikolai; Grün, Christian H.; Jänis, Janne; Scherman, Oren A.; Nau, Werner M.

    2013-05-01

    Inner-phase chemical reactions of guest molecules encapsulated in a macromolecular cavity give fundamental insight into the relative stabilization of transition states by the surrounding walls of the host, thereby modelling the situation of substrates in enzymatic binding pockets. Although in solution several examples of inner-phase reactions are known, the use of cucurbiturils as macrocyclic hosts and bicyclic azoalkanes as guests has now enabled a systematic mass spectrometric investigation of inner-phase reactions in the gas phase, where typically the supply of thermal energy results in dissociation of the supramolecular host-guest assembly. The results reveal a sensitive interplay in which attractive and repulsive van der Waals interactions between the differently sized hosts and guests need to be balanced with a constrictive binding to allow thermally activated chemical reactions to compete with dissociation. The results are important for the understanding of supramolecular reactivity and have implications for catalysis.

  14. Acoustic Instabilities Driven by Slip Between a Condensed Phase and the Gas Phase in Combustion Systems

    NASA Technical Reports Server (NTRS)

    DiCicco, M.; Buckmaster, J.

    1994-01-01

    In the context of gas turbine combustion chambers, this study describes how slip affects the response time of fuel sprays to pressure fluctuations in a gaseous flow field. Slip between the condensed and gas phases is shown to cause fuel vapor mass fraction fluctuations upstream of the reaction zone. A resulting oscillating heat release can drive the pressure fluctuations, depending on the phase difference between them. This generates an acoustic instability. With relevance to previous experimental results, differences are explored in the evaporation characteristics among three different fuel sprays (JP-4, JP-5, and D-2) in relation to their effect on the magnitude of the fuel vapor mass fraction perturbations.

  15. Substituent effects on the gas-phase acidity of silane

    SciTech Connect

    Gordon, M.S.; Volk, D.E. ); Gano, D.R. )

    1989-12-20

    In a previous paper, the gas-phase acidities of XH{sub n} compounds (X = C, N, O, F, Si, P, S, Cl) were predicted with ab initio wave functions. At the MP4{sup 2} level of theory with extended basis sets acidities for these species were determined to be within 2 kcal/mol of experimental value. In the present work, with 6-31G(d) geometries and full MP4/MC-311++G{sup 6}(3df,2pd) energies, the effects of CH{sub 3}, NH{sub 2}, OH, F, SiH{sub 3}, PH{sub 2}, SH, and Cl on the gas-phase acidity of silane are examined. Only a few related calculations have been carried out. All calculations were performed with Gaussian86, and all structures were verified as minima by diagonalizing the analytically determined hessians. Only the valence electrons were correlated in the perturbation theory calculations.

  16. Gas-phase reactivity of ruthenium carbonyl cluster anions.

    PubMed

    Henderson, Matthew A; Kwok, Samantha; McIndoe, J Scott

    2009-04-01

    Partially-ligated anionic ruthenium carbonyl clusters react with alkenes, arenes, and alkanes in the gas phase; the products undergo extensive C-H activation and lose dihydrogen and carbon monoxide under collision-induced dissociation conditions. Triethylsilane and phenylsilane are also reactive towards the unsaturated clusters, and oxygen was shown to rapidly break down the cluster core by oxidative cleavage of the metal-metal bonds. These qualitative gas-phase reactivity studies were conducted using an easily-installed and inexpensive modification of a commercial electrospray ionization mass spectrometer. Interpretation of the large amounts of data generated in these studies is made relatively straightforward by employing energy-dependent electrospray ionization mass spectrometry (EDESI-MS). PMID:19185511

  17. Kinetics of gas phase tetramethyldioxetane decomposition and chemiluminescence

    SciTech Connect

    Cannon, B.D.; Crim, F.F.

    1981-11-04

    Pulsed-laser excitation of overtone vibrations or a weak electronic transition in gas-phase tetramethyldioxetane in combination with temporally and spectrally resolved detection of decomposition product luminescence reveals the presence, along with electronically excited acetone, of an additional emitting species which is not observed in solution studies. The emission is at shorter wavelengths than the acetone phosphorescence, and the emitting species has a zero-pressure decay rate of 0.019 +- 0.014 ..mu..s/sup -1/. The rapid collisional quenching which occurs on roughly every other encounter (k/sub q/ = 5.6 ..mu..s/sup -1/ torr/sup -1/) explains the inability of solution measurements to detect this feature of the tetramethyldioxetane decomposition kinetics. This newly observed component is likely to extend the interpretation of gas-phase decomposition experiments using infrared multiphoton absorption or collisions with fast Xe atoms to excite tetramethyldioxetane.

  18. Ionization of vitamin C in gas phase: Theoretical study.

    PubMed

    Abyar, Fatemeh; Farrokhpour, Hossein

    2016-07-01

    In this work, the gas phase ionization energies and photoelectron spectra of four important conformers of vitamin C were calculated. Symmetry adapted cluster/configuration interaction methodology employing the single and double excitation operators (SAC-CI SD-R) along with D95++(d,p) basis set were used for the calculations. Thermochemistry calculations were also performed on all possible conformers of vitamin C to find the relative stability of conformers in the gas phase. The calculated ionization bands of each conformer were assigned by calculating the contribution of natural bonding orbital (NBO) in the calculated canonical molecular orbitals involved in the ionization. SAC-CI calculations showed that the first ionization band of vitamin C is related to the π electrons of CC bond of the ring of molecule although, there is the lone electron pairs of oxygen atoms and π electrons of CO bond in the molecule. PMID:27092998

  19. Photocatalytic process of simultaneous desulfurization and denitrification of flue gas by TiO2-polyacrylonitrile nanofibers.

    PubMed

    Su, Chunyan; Ran, Xu; Hu, Jianglei; Shao, Changlu

    2013-10-15

    TiO2 nanoparticles were successfully fabricated on electrospun polyacrylonitrile (PAN) nanofibers via the coupling of electrospinning and hydrothermal pathway. A straightforward photocatalysis oxidation process has been developed for simultaneous desulfurization and denitrification of flue gas using the TiO2-PAN photocatalyst. Also, the influences of some important operating parameters, such as titanium loading content of catalyst, flue gas humidity, flue gas flow, and inlet flue gas temperature on removal efficiencies of SO2 and NO were investigated. The results demonstrated that removal efficiencies of 99.3% for SO2 and 71.2% for NO were attained under the following optimal experiment conditions: titanium loading content, 6.78 At %; gas flow rate, 200 mL/min; flue gas humidity, 5%; inlet flue gas temperature, 40 °C. Furthermore, the presumed reaction mechanism of SO2 and NO removal using TiO2-PAN photocatalyst under UV light was proposed. PMID:24024677

  20. Gas phase fractionation method using porous ceramic membrane

    DOEpatents

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

    1996-01-01

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

  1. A varying polytropic gas universe and phase space analysis

    NASA Astrophysics Data System (ADS)

    Khurshudyan, M.

    2016-05-01

    In this paper, we will consider a phenomenological model of a dark fluid that is able to explain an accelerated expansion of our low redshift universe and the phase transition to this accelerated expanding universe. Recent developments in modern cosmology towards understanding of the accelerated expansion of the large scale universe involve various scenarios and approaches. Among these approaches, one of well-known and accepted practice is modeling of the content of our universe via dark fluid. There are various models of dark energy fluid actively studied in recent literature and polytropic gas is among them. In this work, we will consider a varying polytropic gas which is a phenomenological modification of polytropic gas. Our model of varying polytropic dark fluid has been constructed to analogue to a varying Chaplygin gas actively discussed in the literature. We will consider interacting models, where dark matter is a pressureless fluid, to have a comprehensive picture. Phase space analysis is an elegant mathematical tool to earn general understanding of large scale universe and easily see an existence of a solution to cosmological coincidence problem. Imposing some constraints on parameters of the models, we found late time attractors for each case analytically. Cosmological consequences for the obtained late time attractors are discussed.

  2. Gas-Phase Acidities of Phosphorylated Amino Acids.

    PubMed

    Stover, Michele L; Plummer, Chelsea E; Miller, Sean R; Cassady, Carolyn J; Dixon, David A

    2015-11-19

    Gas-phase acidities and heats of formation have been predicted at the G3(MP2)/SCRF-COSMO level of theory for 10 phosphorylated amino acids and their corresponding amides, including phospho-serine (pSer), -threonine (pThr), and -tyrosine (pTyr), providing the first reliable set of these values. The gas-phase acidities (GAs) of the three named phosphorylated amino acids and their amides have been determined using proton transfer reactions in a Fourier transform ion cyclotron mass spectrometer. Excellent agreement was found between the experimental and predicted GAs. The phosphate group is the deprotonation site for pSer and pThr and deprotonation from the carboxylic acid generated the lowest energy anion for pTyr. The infrared spectra were calculated for six low energy anions of pSer, pThr, and pTyr. For deprotonated pSer and pThr, good agreement is found between the experimental IRMPD spectra and the calculated spectra for our lowest energy anion structure. For pTyr, the IR spectra for a higher energy phosphate deprotonated structure is in good agreement with experiment. Additional experiments tested electrospray ionization (ESI) conditions for pTyr and determined that variations in solvent, temperature, and voltage can result in a different experimental GA value, indicating that ESI conditions affect the conformation of the pTyr anion. PMID:26492552

  3. Two-phase, gas-liquid flows in static mixers

    SciTech Connect

    Shah, N.F.; Kale, D.D. )

    1992-02-01

    This paper reports that static mixers are used for many gas-liquid two-phase operations. some of the typical applications are processing of natural gas to remove hydrogen sulfide or carbon dioxide, waste water treatment, dissolution of gases, hydrogenation, chlorination, and so on. They have experimentally studied the pressure drop for oxygen-water system in a bubble column packed with Sulzer-Koch-type mixing elements. They observed that the ratio of pressure drop through the packed bubble column to that through the unpacked one was slightly greater than one. The suitability of static mixers to mix fluids of very widely different viscosities has been demonstrated. Two-phase operations in polymer industry involve very viscous fluids. Due to the high viscosity of these fluids, the flow will be predominantly in laminar region for both fluids. There are no data on gas-liquid two-phase systems incorporating viscous Newtonian and non-Newtonian fluids where flows are predominantly in laminar region.

  4. Parenchymal mechanics, gas mixing, and the slope of phase III.

    PubMed

    Wilson, Theodore A

    2013-07-01

    A model of parenchymal mechanics is revisited with the objective of investigating the differences in parenchymal microstructure that underlie the differences in regional compliance that are inferred from gas-mixing studies. The stiffness of the elastic line elements that lie along the free edges of alveoli and form the boundary of the lumen of the alveolar duct is the dominant determinant of parenchymal compliance. Differences in alveolar size cause parallel shifts of the pressure-volume curve, but have little effect on compliance. However, alveolar size also affects the relation between surface tension and pressure during the breathing cycle. Thus regional differences in alveolar size generate regional differences in surface tension, and these drive Marangoni surface flows that equilibrate surface tension between neighboring acini. Surface tension relaxation introduces phase differences in regional volume oscillations and a dependence of expired gas concentration on expired volume. A particular example of different parenchymal properties in two neighboring acini is described, and gas exchange in this model is calculated. The efficiency of mixing and slope of phase III for the model agree well with published data. This model constitutes a new hypothesis concerning the origin of phase III. PMID:23599394

  5. Gas Phase Model of Surface Reactions for N{2} Afterglows

    NASA Astrophysics Data System (ADS)

    Marković, V. Lj.; Petrović, Z. Lj.; Pejović, M. M.

    1996-07-01

    The adequacy of the homogeneous gas phase model as a representation of the surface losses of diffusing active particles in gas phase is studied. As an example the recent data obtained for the surface recombination coefficients are reanalyzed. The data were obtained by the application of the breakdown delay times which consists of the measurements of the breakdown delay times t_d as a function of the afterglow period tau. It was found that for the conditions of our experiment, the diffusion should not be neglected as the final results are significantly different when obtained by approximate gas phase representation and by exact numerical solution to the diffusion equation. While application of the gas phase effective coefficients to represent surface losses gives an error in the value of the recombination coefficient, it reproduces correctly other characteristics such as order of the process which can be obtained from simple fits to the experimental data. Dans cet article, nous étudions la validité du modèle approximatif représentant les pertes superficielles des particules actives qui diffusent de la phase gazeuse comme pertes dans la phase homogène du gaz. Les données actuelles du coefficient de recombination en surface sont utilisées par cette vérification . Les données experimentales sont obtenues en utilisant la technique qui consiste en la mesure du temps de retard du début de la décharge en fonction de la période de relaxation. Nous avons trouvé que, pour nos conditions expérimentales, la diffusion ne peut être négligée. Aussi, les résultats finals sont considérablement différents quand ils sont obtenus en utilisant le modèle approximatif par comparaison aves les résultats obtenus par la solution numérique exacte de l'équation de la diffusion. L'application des coefficients effectifs dans la phase gaseuse pour la présentation des pertes superficielles donne, pour les coefficients de la recombinaison, des valeurs qui diffèrent en

  6. Carbon Dioxide Separation from Flue Gas by Phase Enhanced Absorption

    SciTech Connect

    Tim Fout

    2007-06-30

    A new process, phase enhanced absorption, was invented. The method is carried out in an absorber, where a liquid carrier (aqueous solution), an organic mixture (or organic compound), and a gas mixture containing a gas to be absorbed are introduced from an inlet. Since the organic mixture is immiscible or at least partially immiscible with the liquid carrier, the organic mixture forms a layer or small parcels between the liquid carrier and the gas mixture. The organic mixture in the absorber improves mass transfer efficiency of the system and increases the absorption rate of the gas. The organic mixture serves as a transportation media. The gas is finally accumulated in the liquid carrier as in a conventional gas-liquid absorption system. The presence of the organic layer does not hinder the regeneration of the liquid carrier or recovery of the gas because the organic layer is removed by a settler after the absorption process is completed. In another aspect, the system exhibited increased gas-liquid separation efficiency, thereby reducing the costs of operation and maintenance. Our study focused on the search of the organic layer or transportation layer to enhance the absorption rate of carbon dioxide. The following systems were studied, (1) CO{sub 2}-water system and CO{sub 2}-water-organic layer system; (2) CO{sub 2}-Potassium Carbonate aqueous solution system and CO{sub 2}-Potassium Carbonate aqueous solution-organic layer system. CO{sub 2}-water and CO{sub 2}-Potassium Carbonate systems are the traditional gas-liquid absorption processes. The CO{sub 2}-water-organic layer and CO{sub 2}-Potassium Carbonate-organic layer systems are the novel absorption processes, phase enhanced absorption. As we mentioned early, organic layer is used for the increase of absorption rate, and plays the role of transportation of CO{sub 2}. Our study showed that the absorption rate can be increased by adding the organic layer. However, the enhanced factor is highly depended on the

  7. Electronic structure calculations of mercury mobilization from mineral phases and photocatalytic removal from water and the atmosphere.

    PubMed

    Da Pieve, Fabiana; Stankowski, Martin; Hogan, Conor

    2014-09-15

    Mercury is a hazardous environmental pollutant mobilized from natural sources, and anthropogenically contaminated and disturbed areas. Current methods to assess mobility and environmental impact are mainly based on field measurements, soil monitoring, and kinetic modelling. In order to understand in detail the extent to which different mineral sources can give rise to mercury release it is necessary to investigate the complexity at the microscopic level and the possible degradation/dissolution processes. In this work, we investigated the potential for mobilization of mercury structurally trapped in three relevant minerals occurring in hot spring environments and mining areas, namely, cinnabar (α-HgS), corderoite (α-Hg3S2Cl2), and mercuric chloride (HgCl2). Quantum chemical methods based on density functional theory as well as more sophisticated approaches are used to assess the possibility of a) direct photoreduction and formation of elemental Hg at the surface of the minerals, providing a path for ready release in the environment; and b) reductive dissolution of the minerals in the presence of solutions containing halogens. Furthermore, we study the use of TiO2 as a potential photocatalyst for decontamination of polluted waters (mainly Hg(2+)-containing species) and air (atmospheric Hg(0)). Our results partially explain the observed pathways of Hg mobilization from relevant minerals and the microscopic mechanisms behind photocatalytic removal of Hg-based pollutants. Possible sources of disagreement with observations are discussed and further improvements to our approach are suggested. PMID:24982025

  8. Photocatalytic, highly hydrophilic porcelain stoneware slabs

    NASA Astrophysics Data System (ADS)

    Raimondo, M.; Guarini, G.; Zanelli, C.; Marani, F.; Fossa, L.; Dondi, M.

    2011-10-01

    Photocatalytic, highly hydrophilic industrial porcelain stoneware large slabs were realized by deposition of nanostructured TiO2 coatings. Different surface finishing and experimental conditions were considered in order to assess the industrial feasibility. Photocatalytic and wetting behaviour of functionalized slabs mainly depends on surface phase composition in terms of anatase/rutile ratio, this involving - as a key issue - the deposition of TiO2 on industrially sintered products with an additional annealing step to strengthen coatings' performances and durability.

  9. Investigation of condensed and early stage gas phase hypergolic reactions

    NASA Astrophysics Data System (ADS)

    Dennis, Jacob Daniel

    Traditional hypergolic propellant combinations, such as those used on the space shuttle orbital maneuvering system first flown in 1981, feature hydrazine based fuels and nitrogen tetroxide (NTO) based oxidizers. Despite the long history of hypergolic propellant implementation, the processes that govern hypergolic ignition are not well understood. In order to achieve ignition, condensed phase fuel and oxidizer must undergo simultaneous physical mixing and chemical reaction. This process generates heat, intermediate condensed phase species, and gas phase species, which then may continue to react and generate more heat until ignition is achieved. The process is not well understood because condensed and gas phase reactions occur rapidly, typically in less than 200 μs, on much faster timescales than traditional diagnostic methods can observe. A detailed understanding of even the gas phase chemistry is lacking, but is critical for model development. Initial research has provided confidence that a study of condensed phase hypergolic reactions is useful and possible. Results obtained using an impinging jet apparatus have shown a critical residence time of 0.3 ms is required for the reaction between monomethylhydrazine (MMH) and red fuming nitric acid (RFNA, ~85% HNO3 + 15% N2O4) to achieve conditions favorable for ignition. This critical residence time spans the time required for liquid phase reactions to occur at the fuel/oxidizer interface and can give some insight into the reaction rates for this propellant combination. Experiments performed in a forced mixing constant volume reactor have demonstrated that the chamber pressurization rate for MMH/RFNA can be significantly reduced by diluting the MMH with deionized water. This result indicates that propellant dilution can slow the chemical reaction rates to occur over observable time scales. The research described in this document consists of two efforts that contribute knowledge to the propulsion community regarding the

  10. Theory of Gas Injection: Interaction of Phase Behavior and Flow

    NASA Astrophysics Data System (ADS)

    Dindoruk, B.

    2015-12-01

    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

  11. Photocatalytic Coatings for Exploration and Spaceport Design

    NASA Technical Reports Server (NTRS)

    2008-01-01

    This project developed self-cleaning photocatalytic coatings that remove contamination without human intervention. The coatings chemically remove organic contaminants and leave no residue. The photocatalyst will not negatively affect other coating properties, especially corrosion resistance. Titanium dioxide, TiO2, is an extremely popular photocatalyst because of its chemical stability, nontoxicity, and low cost. TiO2 is commonly used in the photocatalytic oxidation of organic matter or pollutants in the gas and liquid phases. However, TiO2 does have some drawbacks. It has limited light absorption because of its large band-gap and suffers from a photonic efficiency of less than 10 percent for organic degradation. Dopants can lower the band-gap and improve efficiency. Since the photocatalytically active form of TiO2 is a nanocrystalline powder, it can be difficult to make a robust coating with enough catalyst loading to be effective. Photocatalysts become active when certain light energy is absorbed. When photons with an energy greater than the band-gap, Eg, (wavelengths shorter than 400 nm) impinge upon the surface of the TiO2, an electron-hole pair is formed. The electron-hole pair oxidizes adsorbed substances either directly or via reactive intermediates that form on the surface, such as hydroxyl radicals (OH) or superoxide ions (O2-). Several factors can influence the band-gap energy of TiO2, two of which are crystal structure and impurities. TiO2 exists as three crystal structures brookite, anatase, and rutile that can be controlled via heat treatment. Anatase is the most photocatalytically active crystal form of TiO2. Doping TiO2 with impurities can alter its band-gap energy, as well as its effectiveness as a catalyst. Depending on their size, dopant atoms can occupy either the substitutional or interstitial lattice positions. Atoms that are relatively large will assume the interstitial positions and create a much greater energy disturbance in the crystal than

  12. Gas phase oxidation downstream of a catalytic combustor

    NASA Technical Reports Server (NTRS)

    Tien, J. S.; Anderson, D. N.

    1979-01-01

    Effect of the length available for gas-phase reactions downstream of the catalytic reactor on the emission of CO and unburned hydrocarbons was investigated. A premixed, prevaporized propane/air feed to a 12/cm/diameter catalytic/reactor test section was used. The catalytic reactor was made of four 2.5 cm long monolithic catalyst elements. Four water cooled gas sampling probes were located at positions between 0 and 22 cm downstream of the catalytic reactor. Measurements of unburned hydrocarbon, CO, and CO2 were made. Tests were performed with an inlet air temperature of 800 K, a reference velocity of 10 m/s, pressures of 3 and 600,000 Pa, and fuel air equivalence ratios of 0.14 to 0.24. For very lean mixtures, hydrocarbon emissions were high and CO continued to be formed downstream of the catalytic reactor. At the highest equivalence ratios tested, hydrocarbon levels were much lower and CO was oxidized to CO2 in the gas phase downstream. To achieve acceptable emissions, a downstream region several times longer than the catalytic reactor could be required.

  13. Photo-catalytic activity of Plasmonic Ag@AgCl nanoparticles (synthesized via a green route) for the effective degradation of Victoria Blue B from aqueous phase.

    PubMed

    Devi, Th Babita; Begum, Shamima; Ahmaruzzaman, M

    2016-07-01

    This study reports a green process for the fabrication of Ag@AgCl (silver@silver chloride) nanoparticles by using Aquilaria agallocha (AA) leaves juice without using any external reagents. The effect of various reaction parameters, such as reaction temperature, reaction time and concentration of Aquilaria agallocha leaves juice in the formation of nanoparticles have also been investigated. From the FTIR spectra of leaves juice and phytochemicals test, it was found that flavonoids present in the leaves are responsible for the reduction of Ag(+) ions to Ag(0) species and leads to the formation of Ag@AgCl NPs. The synthesized Ag@AgCl NPs were utilized for the removal of toxic and hazardous dyes, such as Victoria Blue B from aqueous phase. Approximately, 99.46% degradation of Victoria Blue B dye were observed with Ag@AgCl NPs. Furthermore, the photocatalytic activity of the Ag@AgCl nanoparticles was unchanged after 5cycles of operation. PMID:27152674

  14. Template-free preparation of volvox-like Cd(x)Zn(1-x)S nanospheres with cubic phase for efficient photocatalytic hydrogen production.

    PubMed

    Zhou, Hangyue; Liu, Qingyun; Liu, Weimin; Ge, Jiechao; Lan, Minhuan; Wang, Chao; Geng, Jianxin; Wang, Pengfei

    2014-03-01

    Volvox-like Cdx Zn1-x S solid solutions with a cubic zinc blend structure were synthesized through a template-free ethylene glycol process. Cd(Ac)2 ⋅2 H2 O, Zn(Ac)2 ⋅2 H2 O, and thiourea are used as the starting materials and dissolved in ethylene glycol. These reaction precursors and solvent not only contributed to control over the formation of the volvox-like spherical geometry, but also exerted vigorous domination for existence of cubic-phase Cdx Zn1-x S nanostructures. As-prepared volvox-like Cdx Zn1-x S nanospheres have a diameter of around 100 nm with extensional shells. These samples show excellent photocatalytic H2 evolution activity from water splitting under visible-light irradiation without any cocatalyst or scaffolding, owing to their tunable band gap, cubic zinc blend structure, and unique hierarchical porous structure with a high surface area (as high as 95.2 m(2)  g(-1) ). PMID:24403243

  15. Computational phase diagrams of noble gas hydrates under pressure.

    PubMed

    Teeratchanan, Pattanasak; Hermann, Andreas

    2015-10-21

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-Ih, ice-Ic, ice-II, and C0 interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C0 water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C0 hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems. PMID:26493915

  16. Computational phase diagrams of noble gas hydrates under pressure

    NASA Astrophysics Data System (ADS)

    Teeratchanan, Pattanasak; Hermann, Andreas

    2015-10-01

    We present results from a first-principles study on the stability of noble gas-water compounds in the pressure range 0-100 kbar. Filled-ice structures based on the host water networks ice-Ih, ice-Ic, ice-II, and C0 interacting with guest species He, Ne, and Ar are investigated, using density functional theory (DFT) with four different exchange-correlation functionals that include dispersion effects to various degrees: the non-local density-based optPBE-van der Waals (vdW) and rPW86-vdW2 functionals, the semi-empirical D2 atom pair correction, and the semi-local PBE functional. In the He-water system, the sequence of stable phases closely matches that seen in the hydrogen hydrates, a guest species of comparable size. In the Ne-water system, we predict a novel hydrate structure based on the C0 water network to be stable or at least competitive at relatively low pressure. In the Ar-water system, as expected, no filled-ice phases are stable; however, a partially occupied Ar-C0 hydrate structure is metastable with respect to the constituents. The ability of the different DFT functionals to describe the weak host-guest interactions is analysed and compared to coupled cluster results on gas phase systems.

  17. Gas phase contributions to topochemical hydride reduction reactions

    SciTech Connect

    Kobayashi, Yoji; Li, Zhaofei; Hirai, Kei; Tassel, Cédric; Loyer, François; Ichikawa, Noriya; Abe, Naoyuki; Yamamoto, Takafumi; Shimakawa, Yuichi; and others

    2013-11-15

    Alkali and alkali earth hydrides have been used as solid state reductants recently to yield many interesting new oxygen-deficient transition metal oxides. These reactions have tacitly been assumed to be a solid phase reaction between the reductant and parent oxide. We have conducted a number of experiments with physical separation between the reductant and oxides, and find that in some cases reduction proceeds even when the reagents are physically separated, implying reactions with in-situ generated H{sub 2} and, to a lesser extent, getter mechanisms. Our findings change our understanding of these topochemical reactions, and should enhance the synthesis of additional new oxides and nanostructures. - Graphical abstract: Topochemical reductions with hydrides: Solid state or gas phase reaction? Display Omitted - Highlights: • SrFeO{sub 2} and LaNiO{sub 2} were prepared by topochemical reduction of oxides. • Separating the reducing agent (CaH{sub 2}, Mg metal) from the oxide still results in reduction. • Such topochemical reactions can occur in the gas phase.

  18. Computational phase diagrams of noble gas hydrates under pressure

    SciTech Connect

    Teeratchanan, Pattanasak Hermann, Andreas

    2015-10-21

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

  19. Phase-locked measurements of gas-liquid horizontal flows

    NASA Astrophysics Data System (ADS)

    Zadrazil, Ivan; Matar, Omar; Markides, Christos

    2014-11-01

    A flow of gas and liquid in a horizontal pipe can be described in terms of various flow regimes, e.g. wavy stratified, annular or slug flow. These flow regimes appear at characteristic gas and liquid Reynolds numbers and feature unique wave phenomena. Wavy stratified flow is populated by low amplitude waves whereas annular flow contains high amplitude and long lived waves, so called disturbance waves, that play a key role in a liquid entrainment into the gas phase (droplets). In a slug flow regime, liquid-continuous regions travel at high speeds through a pipe separated by regions of stratified flow. We use a refractive index matched dynamic shadowgraphy technique using a high-speed camera mounted on a moving robotic linear rail to track the formation and development of features characteristic for the aforementioned flow regimes. We show that the wave dynamics become progressively more complex with increasing liquid and gas Reynolds numbers. Based on the shadowgraphy measurements we present, over a range of conditions: (i) phenomenological observations of the formation, and (ii) statistical data on the downstream velocity distribution of different classes of waves. EPSRC Programme Grant, MEMPHIS, EP/K0039761/1.

  20. Semiphenomenological model for gas-liquid phase transitions.

    PubMed

    Benilov, E S; Benilov, M S

    2016-03-01

    We examine a rarefied gas with inter-molecular attraction. It is argued that the attraction force amplifies random density fluctuations by pulling molecules from lower-density regions into high-density regions and thus may give rise to an instability. To describe this effect, we use a kinetic equation where the attraction force is taken into account in a way similar to how electromagnetic forces in plasma are treated in the Vlasov model. It is demonstrated that the instability occurs when the temperature T is lower than a certain threshold value T(s) depending on the gas density. It is further shown that, even if T is only marginally lower than T(s), the instability generates clusters with density much higher than that of the gas. These results suggest that the instability should be interpreted as a gas-liquid phase transition, with T(s) being the temperature of saturated vapor and the high-density clusters representing liquid droplets. PMID:27078333

  1. Quantum Control of Femtochemistry in the Gas Phase, Liquid Phase and on Surfaces

    NASA Astrophysics Data System (ADS)

    Gerber, Gustav

    2008-03-01

    By using coherent control techniques we control the behavior of quantum systems on their natural fs-time scale by applying ultrashort coherent light fields in the wavelength range from the IR to the UV. These laser pulses can be variably shaped in space and time using a laser pulse shaper consisting of a liquid-crystal display [1]. Laser-optimized femtochemistry in the gas phase and liquid phase is one field in which this new technique is successfully employed. Automated optimization of branching ratios and total product yields of gas phase photodissociation reactions as well as chemically selective molecular excitation in the liquid phase is performed [2][3]. Structural changes of a molecule in the liquid phase have been controlled by laser-optimized photoisomerization of a cyanine dye molecule [4] and of retinal in bacteriorhodopsin [5]. So far, optimal control techniques have been restricted to gas phase and condensed phase optimization experiments. Recently we have demonstrated femtosecond laser-assisted catalytic reactions on a Pd(100) single crystal surface. By applying a closed-loop optimal control scheme, we manipulate these reactions and selectively optimize the ratio of different bond-forming reaction channels, in contrast to previous quantum control experiments aiming at bond-cleavage. The results represent a first step towards selective photocatalysis of molecules. [1] T. Baumert et al, Appl. Phys. B 65, 779 (1997) [2] A. Assion et al, Science 282, 919(1998); T. Brixner et al, J. Mod. Opt. 50, 539 (2003) [3] T. Brixner et al, Nature, Vol. 414, 57 (2001) and J. Chem. Phys. 118, 3692 (2003) [4] G. Krampert et al, Phys. Rev. Lett. 94, 068305 (2005) [5] G. Vogt et al, Chem. Phys. Lett. 433, 211 (2006) P. Nuernberger et al, Phys. Chem. Chem. Phys. 9, 2470 (2007)

  2. Enhanced photocatalytic activity for degrading pollutants of g-C3N4 by promoting oxygen adsorption after H3BO3 modification

    NASA Astrophysics Data System (ADS)

    Li, Chengming; Raziq, Fazal; Liu, Chong; Li, Zhijun; Sun, Liqun; Jing, Liqiang

    2015-12-01

    The g-C3N4 has been modified by a hydrothermal post treatment with orthoboric acid. It is shown that the surface modification with an appropriate amount of orthoboric acid obviously enhances the surface photovoltage responses of g-C3N4, clearly indicating that the separation of photogenerated charges is greatly improved. This is well responsible for the enhanced photocatalytic activities for degrading representative gas-phase acetaldehyde, and liquid-phase phenol. Moreover, it is demonstrated that the amount of O2 adsorbed on the surfaces of g-C3N4 is greatly increased after H3BO3 modification based on the O2 temperature-programmed desorption curves. It is suggested that the orthoboric acid modification favors O2 adsorption to promote the photogenerated electrons captured for improved photocatalytic activities. This work would provide feasible routes to further improve the photocatalytic performance of semiconductors for degrading pollutants.

  3. Method for predicting photocatalytic oxidation rates of organic compounds.

    PubMed

    Sattler, Melanie L; Liljestrand, Howard M

    2003-01-01

    In designing a photocatalytic oxidation (PCO) system for a given air pollution source, destruction rates for volatile organic compounds (VOCs) are required. The objective of this research was to develop a systematic method of predicting PCO rate constants by correlating rate constants with physical-chemical characteristics of compounds. Accordingly, reaction rate constants were determined for destruction of volatile organics over a titanium dioxide (TiO2) catalyst in a continuous mixed-batch reactor. It was found that PCO rate constants for alkanes and alkenes vary linearly with gas-phase ionization potential (IP) and with gas-phase hydroxyl radical reaction rate constant. The correlations allow rates of destruction of compounds not tested in this research to be predicted based on physical-chemical characteristics. PMID:12568248

  4. Fluorescence Spectroscopy of Gas-phase Polycyclic Aromatic Hydrocarbons

    NASA Technical Reports Server (NTRS)

    Thomas, J. D.; Witt, A. N.

    2006-01-01

    The purpose of this investigation was to produce fluorescence spectra of polycyclic aromatic hydrocarbon (PAH) molecules in the gas-phase for comparison with blue luminescence (BL) emission observed in astrophysical sources Vijh et al. (2004, 2005a,b). The BL occurs roughly from 350 to 450 nm, with a sharp peak near 380 nm. PAHs with three to four rings, e.g. anthracene and pyrene, were found to produce luminescence in the appropriate spectral region, based on existing studies. Relatively few studies of the gas-phase fluorescence of PAHs exist; those that do exist have dealt primarily with the same samples commonly available for purchase such as pyrene and anthracene. In an attempt to understand the chemistry of the nebular environment we also obtained several nitrogen substituted PAHs from our colleagues at NASA Ames. In order to simulate the astrophysical environment we also took spectra by heating the PAHs in a flame. The flame environment counteracts the formation of eximers and permits the spectroscopy of free-flying neutral molecules. Experiments with coal tar demonstrate that fluorescence spectroscopy reveals primarily the presence of the smallest molecules, which are most abundant and which possess the highest fluorescence efficiencies. One gas-phase PAH that seems to fit the BL spectrum most closely is phenanthridine. In view of the results from the spectroscopy of coal tar, a compound containing a mixture of PAHs ranging from small to very large PAH molecules, we can not preclude the presence of larger PAHs in interstellar sources exhibiting BL.

  5. Multiscale Aspects of Modeling Gas-Phase Nanoparticle Synthesis

    PubMed Central

    Buesser, B.; Gröhn, A.J.

    2013-01-01

    Aerosol reactors are utilized to manufacture nanoparticles in industrially relevant quantities. The development, understanding and scale-up of aerosol reactors can be facilitated with models and computer simulations. This review aims to provide an overview of recent developments of models and simulations and discuss their interconnection in a multiscale approach. A short introduction of the various aerosol reactor types and gas-phase particle dynamics is presented as a background for the later discussion of the models and simulations. Models are presented with decreasing time and length scales in sections on continuum, mesoscale, molecular dynamics and quantum mechanics models. PMID:23729992

  6. Gas-phase chemiluminescent reactions of ozone with monoterpenes

    NASA Astrophysics Data System (ADS)

    Arora, P. K.; Chatha, J. P. S.; Vohra, K. G.

    1983-08-01

    Chemiluminescent reactions of ozone with monoterpenes such as linallol, geraniol, d-limonene and α-pinene have been studied in the gas phase at low pressures. Methylglyoxal phosphorescence has been observed in the first two reactions. Emissions from HCHO( 1A 2) and glyoxal ( 3A u) are observed in the reaction of ozone with d-limonene and formation of excited glyoxal is found to be first order in ozone. The reaction of ozone with β-pinene gives rise to emission from a α-dicarbonyl compound and this is found to be first order in ozone. The mechanisms for the formation of excited species are proposed.

  7. The solar system/interstellar medium connection - Gas phase abundances

    NASA Technical Reports Server (NTRS)

    Lutz, Barry L.

    1987-01-01

    Gas-phase abundances in the outer solar system are presented as diagnostics of the interstellar medium at the time of the solar system formation, some 4.55 billion years ago. Possible influences of the thermal and chemical histories of the primitive solar nebula and of the processes which led to the formation and evolution of the outer planets and comets on the elemental and molecular composition of the primordial matter are outlined. The major components of the atmospheres of the outer planets and of the comae of comets are identified, and the cosmogonical and cosmological implications are discussed.

  8. Neurotransmitters in the Gas Phase: La-Mb Studies

    NASA Astrophysics Data System (ADS)

    Cabezas, C.; Mata, S.; López, J. C.; Alonso, J. L.

    2011-06-01

    LA-MB-FTMW spectroscopy combines laser ablation with Fourier transform microwave spectroscopy in supersonic jets overcoming the problems of thermal decomposition associated with conventional heating methods. We present here the results on LA-MB-FTMW studies of some neurotransmitters. Six conformers of dopamine, four of adrenaline, five of noradrenaline and three conformers of serotonin have been characterized in the gas phase. The rotational and nuclear quadrupole coupling constants extracted from the analysis of the rotational spectrum are directly compared with those predicted by ab initio methods to achieve the conclusive identification of different conformers and the experimental characterization of the intramolecular forces at play which control conformational preferences.

  9. Phase diagram of van der Waals-like phase separation in a driven granular gas.

    PubMed

    Khain, Evgeniy; Meerson, Baruch; Sasorov, Pavel V

    2004-11-01

    Equations of granular hydrostatics are used to compute the phase diagram of the recently discovered van der Waals-like phase separation in a driven granular gas. The model two-dimensional system consists of smooth hard disks in a rectangular box, colliding inelastically with each other and driven by a "thermal" wall at zero gravity. The spinodal line and the critical point of the phase separation are determined. Close to the critical point, the spinodal and binodal (coexistence) lines are determined analytically. Effects of the finite size of the confining box in the direction parallel to the thermal wall are investigated. These include suppression of the phase separation by heat conduction in the lateral direction and a change from supercritical to subcritical bifurcation. PMID:15600606

  10. An in-situ synthesis of Ag/AgCl/TiO2/hierarchical porous magnesian material and its photocatalytic performance

    PubMed Central

    Yang, Lu; Wang, Fazhou; Shu, Chang; Liu, Peng; Zhang, Wenqin; Hu, Shuguang

    2016-01-01

    The absorption ability and photocatalytic activity of photocatalytic materials play important roles in improving the pollutants removal effects. Herein, we reported a new kind of photocatalytic material, which was synthesized by simultaneously designing hierarchical porous magnesian (PM) substrate and TiO2 catalyst modification. Particularly, PM substrate could be facilely prepared by controlling its crystal phase (Phase 5, Mg3Cl(OH)5·4H2O), while Ag/AgCl particles modification of TiO2 could be achieved by in situ ion exchange between Ag+ and above crystal Phase. Physiochemical analysis shows that Ag/AgCl/TiO2/PM material has higher visible and ultraviolet light absorption response, and excellent gas absorption performance compared to other controls. These suggested that Ag/AgCl/TiO2/PM material could produce more efficient photocatalytic effects. Its photocatalytic reaction rate was 5.21 and 30.57 times higher than that of TiO2/PM and TiO2/imporous magnesian substrate, respectively. Thus, this material and its intergration synthesis method could provide a novel strategy for high-efficiency application and modification of TiO2 photocatalyst in engineering filed. PMID:26883972

  11. An in-situ synthesis of Ag/AgCl/TiO2/hierarchical porous magnesian material and its photocatalytic performance

    NASA Astrophysics Data System (ADS)

    Yang, Lu; Wang, Fazhou; Shu, Chang; Liu, Peng; Zhang, Wenqin; Hu, Shuguang

    2016-02-01

    The absorption ability and photocatalytic activity of photocatalytic materials play important roles in improving the pollutants removal effects. Herein, we reported a new kind of photocatalytic material, which was synthesized by simultaneously designing hierarchical porous magnesian (PM) substrate and TiO2 catalyst modification. Particularly, PM substrate could be facilely prepared by controlling its crystal phase (Phase 5, Mg3Cl(OH)5·4H2O), while Ag/AgCl particles modification of TiO2 could be achieved by in situ ion exchange between Ag+ and above crystal Phase. Physiochemical analysis shows that Ag/AgCl/TiO2/PM material has higher visible and ultraviolet light absorption response, and excellent gas absorption performance compared to other controls. These suggested that Ag/AgCl/TiO2/PM material could produce more efficient photocatalytic effects. Its photocatalytic reaction rate was 5.21 and 30.57 times higher than that of TiO2/PM and TiO2/imporous magnesian substrate, respectively. Thus, this material and its intergration synthesis method could provide a novel strategy for high-efficiency application and modification of TiO2 photocatalyst in engineering filed.

  12. Photocatalytic efficiencies of self-cleaning glasses. Influence of physical factors.

    PubMed

    Peruchon, L; Puzenat, E; Herrmann, J M; Guillard, C

    2009-07-01

    Two commercial types of self-cleaning glass (SCG) have been tested to confirm the real photocatalytic nature of their properties. This was done by using four photocatalytic tests: (i) in the gas phase with the total oxidation of acetylene; (ii) in water with the total degradation of malic acid, (iii) in water with the total degradation of methylene blue, and (iv) in the solid phase with the total oxidative degradation of a layer of stearic acid deposited on the self-cleaning glass surface, in contact with the superficial titania coating. The influence of various factors (temperature, humidity, wavelength, radiant flux, presence of inorganic particles stuck at the glass surface) was explained in line with the fundamentals of photocatalysis. The results helped to understand the behaviour of self-cleaning glass. PMID:19582281

  13. Printing nanoparticles from the liquid and gas phases using nanoxerography

    NASA Astrophysics Data System (ADS)

    Barry, Chad R.; Steward, Michael G.; Lwin, Nyein Z.; Jacobs, Heiko O.

    2003-10-01

    This paper reports on the directed self-assembly of nanoparticles onto charged surface areas with a resolution of 200 nm from the liquid phase and 100 nm from the gas phase. The charged areas required for this type of nanoxerographic printing were fabricated using a parallel method that employs a flexible, electrically conductive, electrode to charge a thin-film electret. As electrodes, we used metal-coated polymeric stamps and 10 µm thick doped silicon wafers carrying a pattern in topography. Each electrode was brought in contact with a thin-film electret on an n-doped silicon substrate. The charge pattern was transferred into the thin-film electret by applying a voltage pulse between the conductive electrode and the silicon substrate. Areas as large as 1 cm2 were patterned with charge with 100 nm scale resolution in 10 s. These charge patterns attract nanoparticles. A liquid-phase assembly process where electrostatic forces compete with disordering forces due to ultrasonication has been developed to assemble nanoparticles onto charged based receptors in 10 s from a liquid suspension. A gas-phase assembly process was developed that uses a transparent particle assembly module to direct particles towards the charged surface while monitoring the total charge of assembled particles. Nanoparticles were generated using a tube furnace by evaporation and condensation at the outlet. The electrostatically directed assembly of 10-100 nm sized metal (gold, silver) and 30 nm sized carbon particles was accomplished with a resolution 500-1000 times greater than the resolution of existing xerographic printers.

  14. The partitioning of ketones between the gas and aqueous phases

    NASA Astrophysics Data System (ADS)

    Betterton, Eric A.

    Most ketones are not significantly hydrated; they therefore retain their chromophore and they could be photolytically degraded in solution yielding a variety of products including carboxylic acids, aldehydes and radicals. It is difficult to accurately model the partitioning of ketones between the gas phase and aqueous phase because of the lack suitable estimates of the Henry's Law constants; consequently the fate and environmental effects of ketones cannot be confidently predicted. Here we report the experimental determination of the Henry's Law constants of a series of ketones that has yielded a simple straight line equation to predict the Henry's Law constants of simple aliphatic ketones: log H ∗ =0.23Σσ ∗ + 1.51; where H ∗ is the effective Henry's Law constant (M atm -1, and Σσ ∗ is the Taft polar substituents constants. The results for 25°C are (M atm -1) CH 3COCH 3, 32; C 6H 5COCH 3, 110; CH 2ClCOCH 3, 59; CH 3COCOCH 3, 74; CF 3COCH 3, 138. Acetophenone appears to have an abnormally high H ∗. Most low molecular weight aliphatic ketones are predicted to characterized by H ∗⩾30 M atm -1 and therefore they are expected to be found in the aqueous phase at concentrations of ⩾5 - 0.5 μM (given a typical gas-phase concentration range of 1-10 ppbv). The expected rate of decomposition of ketones due to photolysis in hydrometers is briefly discussed.

  15. Gas-phase reactions of cyclopropenylidene with protonated alkyl amines.

    PubMed

    Lin, Ziqing; Tan, Lei; Yang, Yang; Dai, Mingji; Tureček, František; Ouyang, Zheng; Xia, Yu

    2016-04-21

    Vinylidene carbenes (C3H2) are of high interest to interstellar, combustion, and organic chemistry. Due to their high instability, the direct experimental investigation of their chemical reactivity has rarely been achieved. Herein, we report a first study on the reactions of cyclopropenylidene (c-C3H2) with protonated alkyl amines in the gas phase using a home-built ion trap mass spectrometer. The high gas-phase basicity (GB) of ((1)A1) c-C3H2 (calculated as 920 kJ mol(-1)) facilitates the formation of a proton-bound dimer with protonated amines as the first step in the reaction. The dimer can stay as it is or rearrange to a covalent product. The formation of the covalent complex is highly exothermic and its yield is affected by the GB of alkyl amines. The highest yield (82%) was achieved when the GB of the amine was slightly lower but comparable to that of c-C3H2. Our results demonstrate a new reaction pathway of c-C3H2, which has long been considered as a "dead end" in interstellar carbon chemistry. PMID:26978226

  16. Gas-Phase Fragmentation Analysis of Nitro-Fatty Acids

    NASA Astrophysics Data System (ADS)

    Bonacci, Gustavo; Asciutto, Eliana K.; Woodcock, Steven R.; Salvatore, Sonia R.; Freeman, Bruce A.; Schopfer, Francisco J.

    2011-09-01

    Nitro-fatty acids are electrophilic signaling mediators formed in increased amounts during inflammation by nitric oxide and nitrite-dependent redox reactions. A more rigorous characterization of endogenously-generated species requires additional understanding of their gas-phase induced fragmentation. Thus, collision induced dissociation (CID) of nitroalkane and nitroalkene groups in fatty acids were studied in the negative ion mode to provide mass spectrometric tools for their structural characterization. Fragmentation of nitroalkanes occurred mainly through loss of the NO{2/-} anion or neutral loss of HNO2. The CID of nitroalkenes proceeds via a more complex cyclization, followed by fragmentation to nitrile and aldehyde products. Gas-phase fragmentation of nitroalkene functional groups with additional γ or δ unsaturation occurred through a multiple step cyclization reaction process, leading to 5 and 6 member ring heterocyclic products and carbon chain fragmentation. Cyclization products were not obtained during nitroalkane fragmentation, highlighting the role of double bond π electrons during NO{2/-} rearrangements, stabilization and heterocycle formation. The proposed structures, mechanisms and products of fragmentation are supported by analysis of 13C and 15N labeled parent molecules, 6 different nitroalkene positional isomers, 6 nitroalkane positional isomers, accurate mass determinations at high resolution and quantum mechanics calculations. Multiple key diagnostic ion fragments were obtained through this analysis, allowing for the precise placement of double bonds and sites of fatty acid nitration, thus supporting an ability to predict nitro positions in biological samples.

  17. Gas-phase reactivity of novel Ziegler-Natta catalysts

    SciTech Connect

    Alameddin, N.G.; Eyler, J.R.; Richardson, D.E.

    1994-12-31

    The discovery of soluble group 4 metallocene-based catalysts for the Ziegler-Natta polymerization of olefins has generated considerable interest in the field. In particular, the versatility of the Cp (cyclopentadienyl) ligand has made practical the development of a host of novel catalysts which can produce extremely regiospecific and stereospecific polymers. With further improvements in activity and stability, these catalysts are expected to make a major impact on the polymerization industry. Presently, catalyst design is driven by using the steric and electronic properties of the ligands to guide the monomer addition. However, since these ligands have considerable steric bulk, the choice of solvent will significantly affect their catalytic properties. Therefore, an understanding of the intrinsic reactivity of these catalysts independent of a solvent is one of the first steps to building a better catalyst. The work in progress is a study of the reactivity of zircononene-based catalysts in the gas phase. The authors are in the process of studying the rates of reaction of a series of these compounds with H{sub 2} as well as with a number of olefins. In the gas phase, the intrinsic reactivity of these catalysts is revealed and their chemistry can be studied in detail.

  18. Engine exhaust particulate and gas phase contributions to vascular toxicity.

    PubMed

    Campen, Matthew; Robertson, Sarah; Lund, Amie; Lucero, Joann; McDonald, Jacob

    2014-05-01

    Cardiovascular health effects of near-roadway pollution appear more substantial than other sources of air pollution. The underlying cause of this phenomenon may simply be concentration-related, but the possibility remains that gases and particulate matter (PM) may physically interact and further enhance systemic vascular toxicity. To test this, we utilized a common hypercholesterolemic mouse model (Apolipoprotein E-null) exposed to mixed vehicle emission (MVE; combined gasoline and diesel exhausts) for 6 h/d × 50 d, with additional permutations of removing PM by filtration and also removing gaseous species from PM by denudation. Several vascular bioassays, including matrix metalloproteinase-9 protein, 3-nitrotyrosine and plasma-induced vasodilatory impairments, highlighted that the whole emissions, containing both particulate and gaseous components, was collectively more potent than MVE-derived PM or gas mixtures, alone. Thus, we conclude that inhalation of fresh whole emissions induce greater systemic vascular toxicity than either the particulate or gas phase alone. These findings lend credence to the hypothesis that the near-roadway environment may have a more focused public health impact due to gas-particle interactions. PMID:24730681

  19. ENGINE EXHAUST PARTICULATE AND GAS PHASE CONTRIBUTIONS TO VASCULAR TOXICITY

    PubMed Central

    Campen, Matthew; Robertson, Sarah; Lund, Amie; Lucero, Joann; McDonald, Jacob

    2014-01-01

    Cardiovascular health effects of near-roadway pollution appear more substantial than other sources of air pollution. The underlying cause of this phenomenon may simply be concentration-related, but the possibility remains that gases and particulate matter (PM) may physically interact and further enhance systemic vascular toxicity. To test this, we utilized a common hypercholesterolemic mouse model (Apolipoprotein E-null) exposed to mixed vehicular emissions (MVE; combined gasoline and diesel exhausts) for 6 h/d × 50 days, with additional permutations of removing PM by filtration and also removing gaseous species from PM by denudation. Several vascular bioassays, including matrix metalloproteinase 9 (MMP9) protein, 3-nitrotyrosine, and plasma-induced vasodilatory impairments, highlighted that the whole emissions, containing both particulate and gaseous components, was collectively more potent than MVE-derived PM or gas mixtures, alone. Thus, we conclude that inhalation of fresh whole emissions induce greater systemic vascular toxicity than either the particulate or gas phase alone. These findings lend credence to the hypothesis that the near-roadway environment may have a more focused public health impact due to gas-particle interactions. PMID:24730681

  20. Project ARGO: Gas phase formation in simulated microgravity

    NASA Technical Reports Server (NTRS)

    Powell, Michael R.; Waligora, James M.; Norfleet, William T.; Kumar, K. Vasantha

    1993-01-01

    The ARGO study investigated the reduced incidence of joint pain decompression sickness (DCS) encountered in microgravity as compared with an expected incidence of joint pain DCS experienced by test subjects in Earth-based laboratories (unit gravity) with similar protocols. Individuals who are decompressed from saturated conditions usually acquire joint pain DCS in the lower extremities. Our hypothesis is that the incidence of joint pain DCS can be limited by a significant reduction in the tissue gas micronuclei formed by stress-assisted nucleation. Reductions in dynamic and kinetic stresses in vivo are linked to hypokinetic and adynamic conditions of individuals in zero g. We employed the Doppler ultrasound bubble detection technique in simulated microgravity studies to determine quantitatively the degree of gas phase formation in the upper and lower extremities of test subjects during decompression. We found no evidence of right-to-left shunting through pulmonary vasculature. The volume of gas bubble following decompression was examined and compared with the number following saline contrast injection. From this, we predict a reduced incidence of DCS on orbit, although the incidence of predicted mild DCS still remains larger than that encountered on orbit.

  1. Synthesis of Cu nanopowders by condensation from the gas phase

    NASA Astrophysics Data System (ADS)

    Chepkasov, IV; Gafner, Yu Ya; Zobov, K. V.; Batoroev, S. B.; Bardakhanov, S. P.

    2016-02-01

    In order to determine the most efficient regimes of copper nanoparticles synthesis, a series of experiments were conducted by evaporation and subsequent condensation of the raw material in an argon atmosphere. During the tests it was found that an increase of evaporation rate increases significantly the average size of the synthesized particles. However, the study of the dependence of dimensional parameters of the produced clusters on the intensity of the buffer gas flow rate has encountered significant difficulties associated because the results significantly divergent from the previously conducted experiments on the synthesis of transition metal oxides. In order to solve this contradiction the computer simulation was held of copper atoms condensation from the gas phase for the three different cooling rates and for the two final temperatures T = 373 K and T = 77 K. It was found after analysis that the rate of cooling of the gas mixture and the final temperature directly influences the number and the size of particles produced. For instance, with the 10 times of cooling rate decreases the average size of the particles obtained had increased by 2.7 times at a final temperature of 77 K and by 3.1 times at Tf = 373 K.

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

    PubMed

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

    2013-02-19

    Clouds, a key component of the climate system, form when water vapor condenses upon atmospheric particulates termed cloud condensation nuclei (CCN). Variations in CCN concentrations can profoundly impact cloud properties, with important effects on local and global climate. Organic matter constitutes a significant fraction of tropospheric aerosol mass, and can influence CCN activity by depressing surface tension, contributing solute, and influencing droplet activation kinetics by forming a barrier to water uptake. We present direct evidence that two ubiquitous atmospheric trace gases, methylglyoxal (MG) and acetaldehyde, known to be surface-active, can enhance aerosol CCN activity upon uptake. This effect is demonstrated by exposing acidified ammonium sulfate particles to 250 parts per billion (ppb) or 8 ppb gas-phase MG and/or acetaldehyde in an aerosol reaction chamber for up to 5 h. For the more atmospherically relevant experiments, i.e., the 8-ppb organic precursor concentrations, significant enhancements in CCN activity, up to 7.5% reduction in critical dry diameter for activation, are observed over a timescale of hours, without any detectable limitation in activation kinetics. This reduction in critical diameter enhances the apparent particle hygroscopicity up to 26%, which for ambient aerosol would lead to cloud droplet number concentration increases of 8-10% on average. The observed enhancements exceed what would be expected based on Köhler theory and bulk properties. Therefore, the effect may be attributed to the adsorption of MG and acetaldehyde to the gas-aerosol interface, leading to surface tension depression of the aerosol. We conclude that gas-phase surfactants may enhance CCN activity in the atmosphere. PMID:23382211

  3. Feasibility of gas-phase decontamination of gaseous diffusion equipment

    SciTech Connect

    Munday, E.B.; Simmons, D.W.

    1993-02-01

    The five buildings at the K-25 Site formerly involved in the gaseous diffusion process contain 5000 gaseous diffusion stages as well as support facilities that are internally contaminated with uranium deposits. The gaseous diffusion facilities located at the Portsmouth Gaseous Diffusion Plant and the Paducah Gaseous Diffusion Plant also contain similar equipment and will eventually close. The decontamination of these facilities will require the most cost-effective technology consistent with the criticality, health physics, industrial hygiene, and environmental concerns; the technology must keep exposures to hazardous substances to levels as low as reasonably achievable (ALARA). This report documents recent laboratory experiments that were conducted to determine the feasibility of gas-phase decontamination of the internal surfaces of the gaseous diffusion equipment that is contaminated with uranium deposits. A gaseous fluorinating agent is used to fluorinate the solid uranium deposits to gaseous uranium hexafluoride (UF{sub 6}), which can be recovered by chemical trapping or freezing. The lab results regarding the feasibility of the gas-phase process are encouraging. These results especially showed promise for a novel decontamination approach called the long-term, low-temperature (LTLT) process. In the LTLT process: The equipment is rendered leak tight, evacuated, leak tested, and pretreated, charged with chlorine trifluoride (ClF{sub 3}) to subatmospheric pressure, left for an extended period, possibly > 4 months, while processing other items. Then the UF{sub 6} and other gases are evacuated. The UF{sub 6} is recovered by chemical trapping. The lab results demonstrated that ClF{sub 3} gas at subatmospheric pressure and at {approx} 75{degree}F is capable of volatilizing heavy deposits of uranyl fluoride from copper metal surfaces sufficiently that the remaining radioactive emissions are below limits.

  4. Carbon and Noble Gas Isotope Banks in Two-Phase Flow: Changes in Gas Composition During Migration

    NASA Astrophysics Data System (ADS)

    Sathaye, K.; Larson, T.; Hesse, M. A.

    2015-12-01

    In conjunction with the rise of unconventional oil and gas production, there has been a recent rise in interest in noble gas and carbon isotope changes that can occur during the migration of natural gas. Natural gas geochemistry studies use bulk hydrocarbon composition, carbon isotopes, and noble gas isotopes to determine the migration history of gases from source to reservoir, and to trace fugitive gas leaks from reservoirs to shallow groundwater. We present theoretical and experimental work, which helps to explain trends observed in gas composition in various migration scenarios. Noble gases are used as tracers for subsurface fluid flow due to distinct initial compositions in air-saturated water and natural gases. Numerous field studies have observed enrichments and depletions of noble gases after gas-water interaction. A theoretical two-phase gas displacement model shows that differences in noble gas solubility will cause volatile gas components will become enriched at the front of gas plumes, leaving the surrounding residual water stripped of dissolved gases. Changes in hydrocarbon gas composition are controlled by gas solubility in both formation water and residual oil. In addition to model results, we present results from a series of two-phase flow experiments. These results demonstrate the formation of a noble gas isotope banks ahead of a main CO2 gas plume. Additionally, we show that migrating hydrocarbon gas plumes can sweep biogenic methane from groundwater, significantly altering the isotope ratio of the gas itself. Results from multicomponent, two-phase flow experiments qualitatively agree with the theoretical model, and previous field studies. These experimentally verified models for gas composition changes can be used to aid source identification of subsurface gases.

  5. Specific, trace gas induced phase transition in copper(II)oxide for highly selective gas sensing

    NASA Astrophysics Data System (ADS)

    Kneer, J.; Wöllenstein, J.; Palzer, S.

    2014-08-01

    Here, we present results on the investigation of the percolation phase transition in copper(II)oxide (CuO) and show how it may be used to determine trace gas concentrations. This approach provides a highly selective sensing mechanism for the detection of hydrogen sulfide even in oxygen depleted atmospheres. In real-world applications, this scenario is encountered in biogas plants and natural gas facilities, where reliable H2S sensing and filtering are important because of the destructive effects H2S has on machinery. As opposed to gas detection via standard metal-oxide reaction routes, the percolation dynamics are demonstrated to be independent of the surface morphology in accordance with the universality of phase transitions. The sensing behavior of ink-jet printed CuO layers was tested for a large set of parameters including layer temperature, hydrogen sulfide (H2S) and oxygen concentration, as well as the sensitivity towards other gas species. The electrical percolation of the sensing layer is heralded by a dramatic drop in the overall resistivity of the CuO layer for temperatures below 200 °C. The observed percolation phenomena in this temperature regime are unique to H2S even in comparison with related volatile thio-compounds making the sensing mechanism highly selective. At elevated temperatures above 300 °C, the phase transition does not occur. This enables two distinct operational modes which are tunable via the sensor temperature and also allows for resetting the sensing layer after an electrical breakthrough.

  6. Singular effect of crystallite size on the charge carrier generation and photocatalytic activity of nano-TiO2

    NASA Astrophysics Data System (ADS)

    Strauss, Mathias; Pastorello, Murilo; Sigoli, Fernando A.; Silva, Juliana M. de Souza e.; Mazali, Italo O.

    2014-11-01

    Photocatalytic processes on nanometric titanium oxide have been extensively studied from the standpoint of solar energy utilization and remediation of water and gas streams polluted with organic molecules. It is accepted that TiO2 crystallite size and crystalline phase are among the parameters involved in the control of the photocatalytic activity. However, while changing the catalyst nanoparticle size, other attributes important to assess photocatalytic activity may be modified, making thus difficult to define to which extension the photoactivity changes are related only to size differences. Therefore, aiming at studying exclusively the size effect and the parameters directly related to size on the photocatalytic activity of nanometric TiO2, in this work it was explored a method to synthesize TiO2 nanoparticles with controlled size, highly similar morphology and comparable phase and degree of crystallinity. A set composed of four samples of nano-TiO2 loaded porous Vycor glass, each sample having a specific TiO2 nanoparticle size, was tested on the photoactivated process of depollution of solutions of salicylic acid and methylene blue. The photocatalytic activity observed for the organic compounds tested was inversely proportional to the TiO2 nanoparticle size. An opposite tendency was observed for the generation of OH radicals during photocatalyst illumination, as more radicals are formed on the material containing the larger TiO2 nanoparticles. Results of this study suggest that photocatalytic activity of nano-TiO2 is less favored by the enhanced light absorption response and the higher generation of oxidative species observed for the larger nanoparticles. Better catalysts were obtained when nano-TiO2 exhibited high surface-to-volume ratio and had small recombination volumes, which respectively favors pollutant adsorption-desorption on catalyst surface and reduce the number of recombined charge carriers.

  7. Application of Phase-field Method in Predicting Gas Bubble Microstructure Evolution in Nuclear Fuels

    SciTech Connect

    Hu, Shenyang Y.; Li, Yulan; Sun, Xin; Gao, Fei; Devanathan, Ramaswami; Henager, Charles H.; Khaleel, Mohammad A.

    2010-04-30

    Fission product accumulation and gas bubble microstructure evolution in nuclear fuels strongly affect thermo-mechanical properties such as thermal conductivity, gas release, volumetric swelling and cracking, and hence the fuel performance. In this paper, a general phase-field model is developed to predict gas bubble formation and evolution. Important materials processes and thermodynamic properties including the generation of gas atoms and vacancies, sinks for vacancies and gas atoms, the elastic interaction among defects, gas re-solution, and inhomogeneity of elasticity and diffusivity are accounted for in the model. The simulations demonstrate the potential application of the phase-field method in investigating 1) heterogeneous nucleation of gas bubbles at defects; 2) effect of elastic interaction, inhomogeneity of material properties, and gas re-solution on gas bubble microstructures; and 3) effective properties from the output of phase-field simulations such as distribution of defects, gas bubbles, and stress fields.

  8. Conformational Study of Taurine in the Gas Phase

    NASA Astrophysics Data System (ADS)

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

    2009-08-01

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

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

    PubMed

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

    2014-12-19

    Highly magnetic metal Co nanoparticles were produced via reducing flame spray pyrolysis, and directly coated with an epoxy polymer in flight. The polymer content in the samples varied between 14 and 56 wt% of nominal content. A homogenous dispersion of Co nanoparticles in the resulting nanocomposites was visualized by electron microscopy. The size and crystallinity of the metallic fillers was not affected by the polymer, as shown by XRD and magnetic hysteresis measurements. The good control of the polymer content in the product nanocomposite was shown by elemental analysis. Further, the successful polymerization in the gas phase was demonstrated by electron microscopy and size measurements. The presented effective, dry and scalable one-step synthesis method for highly magnetic metal nanoparticle/polymer composites presented here may drastically decrease production costs and increase industrial yields. PMID:25422410

  10. Reduced-background gas-phase absorption spectroscopy.

    PubMed

    Sweetser, J N; Trebino, R

    1998-08-15

    We propose and demonstrate a new method for single-shot multiplex absorption spectroscopy that permits enhanced sensitivity in the simultaneous measurement of multiple spectral lines in rapidly changing gas-phase media, such as turbulent flames. It uses an ultrashort laser pulse that propagates through the absorbing medium, for which the relevant absorption information resides in the free-induction decay that is trailing behind the transmitted pulse. Time gating out most of the transmitted pulse, but not the free-induction decay, enhances the relative fraction of light that contains absorption information when the spectrum is measured. This procedure reduces the background associated with the input light, thus enhancing detection sensitivity. PMID:18087501

  11. Gas-phase interaction of protonated lysine with water

    NASA Astrophysics Data System (ADS)

    Rozman, Marko; Srzic, Dunja; Klasinc, Leo

    2006-07-01

    Gas-phase interaction of LysH+ with D2O has been investigated in order to elucidate the H/D exchange reaction mechanism and possibility of water assisted ion-zwitterion structure formation. The proceed of the interaction is modeled by DFT calculations. Potential energy profiles for: the perturbation from ion-molecule to ion-zwitterion structure, the "flip-flop" and the "bridging" mechanism are presented. Analysis of H/D exchange kinetics results for LysH+ with D2O and CD3OD measured in a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer agree with ion-molecule structure of LysH+. Both experimental and theoretical findings suggest that during interaction of LysH+ with D2O isotopic exchange is favored over the water assisted conformational change from ion-molecule into ion-zwitterion structure.

  12. Dissociative attachment reactions of electrons with gas phase superacids

    SciTech Connect

    Liu, X.

    1992-01-01

    Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients [beta] for reactions of electrons with gas phase superacids HCo(PF[sub 3])[sub 4], HRh(PF[sub 3])[sub 4] and carbonyl hydride complexes HMn(CO)[sub 5], HRe(CO)[sub 5] have been determined under thermal conditions over the approximate temperature range 300[approximately]550 K. The superacids react relatively slowly (<1/20 of [beta][sub max]) with free electrons in a thermal plasma, and the values of [beta] obtained this far do not show a correlation between acidity and [beta]. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; it was found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF[sub 3])[sub 4] was found to be independent of temperature even though the [beta][HCo(PF[sub 3])[sub 4

  13. Silicon Nanowire-Based Devices for Gas-Phase Sensing

    PubMed Central

    Cao, Anping; Sudhölter, Ernst J.R.; de Smet, Louis C.P.M.

    2014-01-01

    Since their introduction in 2001, SiNW-based sensor devices have attracted considerable interest as a general platform for ultra-sensitive, electrical detection of biological and chemical species. Most studies focus on detecting, sensing and monitoring analytes in aqueous solution, but the number of studies on sensing gases and vapors using SiNW-based devices is increasing. This review gives an overview of selected research papers related to the application of electrical SiNW-based devices in the gas phase that have been reported over the past 10 years. Special attention is given to surface modification strategies and the sensing principles involved. In addition, future steps and technological challenges in this field are addressed. PMID:24368699

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

    NASA Technical Reports Server (NTRS)

    Constantinescu, Ileana C.; Qi, Nan; LeVan, M. Douglas; Finn, Cory K.; Finn, John E.; Luna, Bernadette (Technical Monitor)

    2000-01-01

    A regenerable air purification system (RAPS) that uses water vapor to displace adsorbed contaminants from an. adsorbent column into a closed oxidation loop is under development through cooperative R&D between Vanderbilt University and NASA Ames Research Center. A unit based on this design can be used for removing trace gas-phase contaminants from spacecraft cabin air or from polluted process streams including incinerator exhaust. Recent work has focused on fabrication and operation of a RAPS breadboard at NASA Ames, and on measurement of adsorption isotherm data for several important organic compounds at Vanderbilt. These activities support the use and validation of RAPS modeling software also under development at Vanderbilt, which will in turn be used to construct a prototype system later in the project.

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

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

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

  16. Infrared photodissociation spectroscopy of protonated neurotransmitters in the gas phase

    NASA Astrophysics Data System (ADS)

    MacLeod, N. A.; Simons, J. P.

    2007-03-01

    Protonated neurotransmitters have been produced in the gas phase via a novel photochemical scheme: complexes of the species of interest, 1-phenylethylamine, 2-amino-1-phenylethanol and the diastereo-isomers, ephedrine and pseudoephedrine, with a suitable proton donor, phenol (or indole), are produced in a supersonic expansion and ionized by resonant two photon ionization of the donor. Efficient proton transfer generates the protonated neurotransmitters, complexed to a phenoxy radical. Absorption of infrared radiation, and subsequent evaporation of the phenoxy tag, coupled with time of flight mass spectrometry, provides vibrational spectra of the protonated (and also hydrated) complexes for comparison with the results of quantum chemical computation. Comparison with the conformational structures of the neutral neurotransmitters (established previously) reveals the effect of protonation on their structure. The photochemical proton transfer strategy allows spectra to be recorded from individual laser shots and their quality compares favourably with that obtained using electro-spray or matrix assisted laser desorption ion sources.

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

    SciTech Connect

    Nathan Robert Classen

    2002-12-31

    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 {beta} C-H insertion mechanism.

  18. Photocatalytic water splitting

    NASA Astrophysics Data System (ADS)

    Kuo, Yenting

    New photocatalystic materials Ti-In oxy(nitride) and nanosized Ru-loaded strontium titanate doped with Rh (Ru/SrTiO3:Rh) have been synthesized. The textural and surface characteristic properties were studied by nitrogen BET analysis, diffuse reflectance UV-vis spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy and powder XRD. The photocatalytic properties were enhanced by the binary metal oxides of titanium dioxide and indium oxide. The XRD patterns confirmed the oxygen exchange between two metal oxides during the synthesis. Moreover, the presence of titanium dioxide can help the stabilization of InN during hot NH3(g) treatment. On the other hand, the particle sizes of aerogel prepared Ru/SrTiO3:Rh varied from 12 to 25 nm depended on different Rh doping. A mixture of ethanol and toluene was found to be the best binary solvent for supercritical drying, which yielded a SrTiO3 sample with a surface area of 130 m2/g and an average crystallite size of 6 nm. Enhanced photocatalytic hydrogen production under UV-vis light irradiation was achieved by ammonolysis of intimately mixed titanium dioxide and indium oxide at high temperatures. Gas chromatography monitored steadily the formation of hydrogen when sacrificial (methanol or ethanol) were present. XRD patterns confirmed that the photocatalysts maintain crystalline integrity before and after water splitting experiments. Moreover, the presence of InN may be crucial for the increase of hydrogen production activities. These Ru/SrTiO3:Rh photocatalysts have been studied for photocatalytic hydrogen production under visible light. The band gap of the bulk SrTiO 3 (3.2 eV) does not allow response to visible light. However, after doping with rhodium and loaded with ruthenium, the modified strontium titanates can utilize light above 400 nm due to the formation of valence band or electron donor levels inside of the band gap. Moreover, the surface areas of these

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

    PubMed Central

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

    2013-01-01

    Clouds, a key component of the climate system, form when water vapor condenses upon atmospheric particulates termed cloud condensation nuclei (CCN). Variations in CCN concentrations can profoundly impact cloud properties, with important effects on local and global climate. Organic matter constitutes a significant fraction of tropospheric aerosol mass, and can influence CCN activity by depressing surface tension, contributing solute, and influencing droplet activation kinetics by forming a barrier to water uptake. We present direct evidence that two ubiquitous atmospheric trace gases, methylglyoxal (MG) and acetaldehyde, known to be surface-active, can enhance aerosol CCN activity upon uptake. This effect is demonstrated by exposing acidified ammonium sulfate particles to 250 parts per billion (ppb) or 8 ppb gas-phase MG and/or acetaldehyde in an aerosol reaction chamber for up to 5 h. For the more atmospherically relevant experiments, i.e., the 8-ppb organic precursor concentrations, significant enhancements in CCN activity, up to 7.5% reduction in critical dry diameter for activation, are observed over a timescale of hours, without any detectable limitation in activation kinetics. This reduction in critical diameter enhances the apparent particle hygroscopicity up to 26%, which for ambient aerosol would lead to cloud droplet number concentration increases of 8–10% on average. The observed enhancements exceed what would be expected based on Köhler theory and bulk properties. Therefore, the effect may be attributed to the adsorption of MG and acetaldehyde to the gas–aerosol interface, leading to surface tension depression of the aerosol. We conclude that gas-phase surfactants may enhance CCN activity in the atmosphere. PMID:23382211

  20. Hydration of potassiated amino acids in the gas phase.

    PubMed

    Wincel, Henryk

    2007-12-01

    The thermochemistry of stepwise hydration of several potassiated amino acids was studied by measuring the gas-phase equilibria, AAK(+)(H(2)O)(n-1) + H(2)O = AAK(+)(H(2)O)(n) (AA = Gly, AL, Val, Met, Pro, and Phe), using a high-pressure mass spectrometer. The AAK(+) ions were obtained by electrospray and the equilibrium constants K(n-1,n) were measured in a pulsed reaction chamber at 10 mbar bath gas, N(2), containing a known partial pressure of water vapor. Determination of the equilibrium constants at different temperatures was used to obtain the DeltaH(n)(o), DeltaS(n)(o), and DeltaG(n)(o) values. The results indicate that the water binding energy in AAK(+)(H(2)O) decreases as the K(+) affinity to AA increases. This trend in binding energies is explained in terms of changes in the side-chain substituent, which delocalize the positive charge from K(+) to AA in AAK(+) complexes, varying the AAK(+)-H(2)O electrostatic interaction. PMID:17928233

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

    SciTech Connect

    Tuerler, A.; Gregorich, K.E.; Czerwinski, K.R.; Hannink, N.J.; Henderson, R.A.; Hoffman, D.C.; Kacher, C.D.; Kadkhodayan, B.; Kreek, S.A.; Lee, D.M.; Leyba, J.D.; Nurmia, M.J. ); Gaeggeler, H.W.; Jost, D.T.; Kovacs, J.; Scherer, U.W.; Vermeulen, D.; Weber, A. , Villigen ); Barth, H.; Gober, M.K.; Kratz, J.V. (Philipps-Univ., Marburg

    1991-04-01

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

  2. Gas phase plasma impact on phenolic compounds in pomegranate juice.

    PubMed

    Herceg, Zoran; Kovačević, Danijela Bursać; Kljusurić, Jasenka Gajdoš; Jambrak, Anet Režek; Zorić, Zoran; Dragović-Uzelac, Verica

    2016-01-01

    The aim of the study was to evaluate the effect of gas phase plasma on phenolic compounds in pomegranate juice. The potential of near infrared reflectance spectroscopy combined with partial least squares for monitoring the stability of phenolic compounds during plasma treatment was explored, too. Experiments are designed to investigate the effect of plasma operating conditions (treatment time 3, 5, 7 min; sample volume 3, 4, 5 cm(3); gas flow 0.75, 1, 1.25 dm(3) min(-1)) on phenolic compounds and compared to pasteurized and untreated pomegranate juice. Pasteurization and plasma treatment resulted in total phenolic content increasing by 29.55% and 33.03%, respectively. Principal component analysis and sensitivity analysis outputted the optimal treatment design with plasma that could match the pasteurized sample concerning the phenolic stability (5 min/4 cm(3)/0.75 dm(3) min(-1)). Obtained results demonstrate the potential of near infrared reflectance spectroscopy that can be successfully used to evaluate the quality of pomegranate juice upon plasma treatment considering the phenolic compounds. PMID:26213024

  3. Gas phase hydrogen permeation in alpha titanium and carbon steels

    NASA Technical Reports Server (NTRS)

    Johnson, D. L.; Shah, K. K.; Reeves, B. H.; Gadgeel, V. L.

    1980-01-01

    Commercially pure titanium and heats of Armco ingot iron and steels containing from 0.008-1.23 w/oC were annealed or normalized and machined into hollow cylinders. Coefficients of diffusion for alpha-Ti and alpha-Fe were determined by the lag-time technique. Steady state permeation experiments yield first power pressure dependence for alpha-Ti and Sievert's law square root dependence for Armco iron and carbon steels. As in the case of diffusion, permeation data confirm that alpha-titanium is subject to at least partial phase boundary reaction control while the steels are purely diffusion controlled. The permeation rate in steels also decreases as the carbon content increases. As a consequence of Sievert's law, the computed hydrogen solubility decreases as the carbon content increases. This decreases in explained in terms of hydrogen trapping at carbide interfaces. Oxidizing and nitriding the surfaces of alpha-titanium membranes result in a decrease in the permeation rate for such treatment on the gas inlet surfaces but resulted in a slight increase in the rate for such treatment on the gas outlet surfaces. This is explained in terms of a discontinuous TiH2 layer.

  4. Substrate-free gas-phase synthesis of graphene

    NASA Astrophysics Data System (ADS)

    Dato, Albert Manglallan

    Graphene is a single atomic layer of sp2-bonded carbon atoms tightly packed in a two-dimensional honeycomb lattice. The material possesses remarkable properties and has been envisioned for use in numerous applications. Contemporary graphene production techniques require substrates or graphite crystals to create graphene. Furthermore, these approaches involve multiple steps, and sometimes non-ambient conditions, to produce atomically-thin sheets. This dissertation presents the first substrate-free gas-phase graphene synthesis method. The technique can synthesize graphene in a single step at atmospheric pressure, without the use of graphite or substrates. The novel synthesis method was discovered through experiments that tested the hypothesis that graphene could be synthesized through the delivery of alcohols into argon plasmas. The experiments presented in this dissertation were conducted in an atmospheric-pressure microwave plasma reactor. Solid carbon materials were produced by delivering liquid ethanol droplets directly into argon plasmas. Numerous characterization techniques were used to unambiguously prove that the synthesized materials were clean and highly ordered graphene sheets. Additional studies investigated the effects of variable experimental parameters on the graphene synthesis process. The applied microwave power did not significantly affect the types of structures produced in the reactor. Lowering the volumetric flow rate of the plasma gas resulted in the synthesis of graphitic particles. The composition of the precursors delivered into the reactor also affected graphene synthesis. Graphene was not produced through the delivery of methanol or isopropyl alcohol droplets. However, graphene was obtained through dimethyl ether, which is an organic compound with the same atomic composition as ethanol. Thus, the flow rate and precursor composition significantly affected the nucleation, growth, and residence time of the materials created during experiments

  5. Tracking Gas Phase Composition in Oil evaporation and Oxidation Experiments

    NASA Astrophysics Data System (ADS)

    Amador-Muñoz, O.; Zhang, H.; Misztal, P. K.; Worton, D.; Drozd, G.; Goldstein, A. H.

    2015-12-01

    Primary Organic Aerosol (POA) is emitted directly by anthropogenic or natural sources, whereas Secondary Organic Aerosol (SOA) is formed in the atmosphere through chemical reactions that result from conversion of more volatile species into lower volatility oxidized products and their subsequent condensation to the particulate phase. We studied SOA formation from evaporation of Macondo crude oil (MC 252) using a wind tunnel coupled to a flow tube oxidation reactor. Ozone, UV lights, and water vapor were used to make OH radicals. Organic compounds in the gas phase, both those evaporated from the wind tunnel and those formed in the flow tube oxidation experiments, were monitored using proton-transfer-reaction mass spectrometry (PTR-qMS and PTR-TOF-MS). We observed approximately 400 different species. Compounds with less than C10 were mostly evaporated in the first 5 hours when maximum SOA formation was also obtained. Hydrocarbons with carbon number (11-14) were still present in the oil after 12 h of continuous evaporation at wind speed of 2 m s-1. We will show the implications of these results for the production of SOA related to the range of evaporated chemical size and reactivity.

  6. Gas phase synthesis of two ensembles of silicon nanoparticles

    NASA Astrophysics Data System (ADS)

    Mohan, A.; de Jong, M. M.; Poulios, I.; Schropp, R. E. I.; Rath, J. K.

    2015-09-01

    Dusty plasmas provide a very favorable environment for the growth of silicon nanocrystals. For application of silicon nanocrystals in a solar cell, the fabrication of monodisperse silicon quantum dots has been challenging. We report a single step method to synthesize silicon (Si) nanoparticles in a custom designed dedicated plasma reactor. The nanoparticles produced in the gas phase belong to two different phases exhibiting different structural and optical properties. Particles made in the bulk of the plasma are aggregates of crystalline particles with a mean size of 100 nm. Particles made in locally enhanced plasma regions produced at holes present in the grounded electrode contain free-standing quantum sized particles with crystallites (with mean size of 2.95 nm) embedded within an amorphous matrix. We provide insight on different plasma processes leading to the formation of aggregates and free-standing particles. We hypothesize that the free standing particles are formed due to the excess energetic electrons present in locally enhanced discharges.

  7. Full field gas phase velocity measurements in microgravity

    NASA Technical Reports Server (NTRS)

    Griffin, Devon W.; Yanis, William

    1995-01-01

    Measurement of full-field velocities via Particle Imaging Velocimetry (PIV) is common in research efforts involving fluid motion. While such measurements have been successfully performed in the liquid phase in a microgravity environment, gas-phase measurements have been beset by difficulties with seeding and laser strength. A synthesis of techniques developed at NASA LeRC exhibits promise in overcoming these difficulties. Typical implementation of PIV involves forming the light from a pulsed laser into a sheet that is some fraction of a millimeter thick and 50 or more millimeters wide. When a particle enters this sheet during a pulse, light scattered from the particle is recorded by a detector, which may be a film plane or a CCD array. Assuming that the particle remains within the boundaries of the sheet for the second pulse and can be distinguished from neighboring particles, comparison of the two images produces an average velocity vector for the time between the pulses. If the concentration of particles in the sampling volume is sufficiently large but the particles remain discrete, a full field map may be generated.

  8. Atomic and molecular physics in the gas phase

    SciTech Connect

    Toburen, L.H.

    1990-09-01

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

  9. Band alignment and enhanced photocatalytic activation of α/β-Bi2O3 heterojunctions via in situ phase transformation.

    PubMed

    Shan, Lianwei; Wang, Guilin; Li, Dan; San, Xingyuan; Liu, Lizhu; Dong, Limin; Wu, Ze

    2015-05-01

    The assembling heterojunction, one of the key topics in photocatalysts and semiconductors (SCs), is generally accomplished in at least two steps, of which the first step is the synthesis of a matrix, and then the growth of the second phase on the matrix. Herein we present the preparation of α/β-Bi2O3 heterojunctions by an in situ phase transformation technique. Under normal pressure, a facile citrate method was used to synthesize β-Bi2O3 nanosheets and α/β-Bi2O3 heterojunctions. The novel features of the process are the mild operating conditions by an appropriate selection of heat treatment temperature and time. Using transmission electron microscopy (TEM), we found that a number of nano-sized α-Bi2O3 form on the β-Bi2O3 nanosheet via a controlled β→α phase transition, generating a large number of heterojunctions. The CM1 (calcining β-Bi2O3 precursor at 363 °C for 4 h) heterojunction achieves a strong visible light absorption and dye absorption capacity and produces a very high reaction rate for Rhodamine B (RhB) photodegradation. Electrochemical impedance spectroscopy (EIS) revealed excellent charge transfer characteristics of the heterojunction, which accounts for its high photoactivity. Using the X-ray electron valence band spectra, it is found that the valence band of α-Bi2O3 is more negative than that of β-Bi2O3. Thus, in heterojunctions, the photogenerated holes in β-Bi2O3 are transferred to α-Bi2O3 with good charge transport characteristics by the intrinsic driving force in the interface field. Furthermore, a separated hole can accomplish a transfer process from α-Bi2O3 to the aqueous solution within its lifetime due to the diameter of α-Bi2O3 being less than 17.6 nm. PMID:25820418

  10. Tricrystalline TiO2 with enhanced photocatalytic activity and durability for removing volatile organic compounds from indoor air.

    PubMed

    Chen, Kunyang; Zhu, Lizhong; Yang, Kun

    2015-06-01

    It is important to develop efficient and economic techniques for removing volatile organic compounds (VOCs) in indoor air. Heterogeneous TiO2-based semiconductors are a promising technology for achieving this goal. Anatase/brookite/rutile tricrystalline TiO2 with mesoporous structure was synthesized by a low-temperature hydrothermal route in the presence of HNO3. The obtained samples were characterized by X-ray diffraction and N2 adsorption-desorption isotherm. The photocatalytic activity was evaluated by photocatalytic decomposition of toluene in air under UV light illumination. The results show that tricrystalline TiO2 exhibited higher photocatalytic activity and durability toward gaseous toluene than bicrystalline TiO2, due to the synergistic effects of high surface area, uniform mesoporous structure and junctions among mixed phases. The tricrystalline TiO2 prepared at RHNO3=0.8, containing 80.7% anatase, 15.6% brookite and 3.7% rutile, exhibited the highest photocatalytic activity, about 3.85-fold higher than that of P25. The high activity did not significantly degrade even after five reuse cycles. In conclusion, it is expected that our study regarding gas-phase degradation of toluene over tricrystalline TiO2 will enrich the chemistry of the TiO2-based materials as photocatalysts for environmental remediation and stimulate further research interest on this intriguing topic. PMID:26040745

  11. Phase transition dynamics of liquid phase precipitation from a supersaturated gas mixture.

    PubMed

    Pines, V; Zlatkowski, M; Chait, A

    2004-11-01

    This work presents a self-consistent description of phase transition dynamics of disperse liquid phase precipitating from a supersaturated gas mixture. The unified approach integrates the macroscale transport phenomena of cloud dynamics with the essential microphysical kinetic processes of droplet condensation, evaporation, and droplet collisions simultaneously taking place in stochastic population of liquid droplets. A complete set of governing equations with well-defined dissipative fluxes and kinetic rates is derived for phase transition dynamics from nucleation to postnucleation to coarsening stages. The local thermodynamics of precipitating system, which is considered as ternary mixture of disperse liquid phase and water vapor with dry air, is redefined to explicitly include on equal basis both the vapor content and liquid content into the fundamental thermodynamic relations and equation of state. The molecular kinetic flux regularization method for growth of submicron droplets is reexamined to include, among others, significant contribution of vapor molecular energy flux into total heat flux, resulting in new expressions for the droplet temperature, growth rate, and effective diffusion coefficients. The local kinetic rates are determined on the basis of microscale kinetic equation for the droplet distribution function. This is in contrast to commonly used semiempirical parametrization schemes for kinetic rates with adjustable parameters, wherein the probabilistic aspects of microphysical processes are not rigorously addressed. Stochastic diffusion interactions among droplets competing for the available water vapor and modifications in the kinetic equation for droplets growing in stochastic population with direct long-range diffusion interactions amongst them are discussed and formulated as well. PMID:15527359

  12. Measurement of Gas-phase Acids in Diesel Exhaust

    NASA Astrophysics Data System (ADS)

    Wentzell, J. J.; Liggio, J.; Li, S.; Vlasenko, A. L.; Staebler, R. M.; Brook, J.; Lu, G.; Poitras, M.; Chan, T.

    2012-12-01

    Gas-phase acids were measured using chemical ionization mass spectrometry (CIMS) as part of the Diesel Engine Emission Research Experiment (DEERE). The CIMS technique, utilizing acetate ion (CH3COO-) as a reagent ion, proved to be a rapid (measurements on the order of seconds) and sensitive (several counts/pptv) method of quantifying the acid emissions. Diluted diesel exhaust measurements were made from a Constant Volume Sampling dilution tunnel using a light duty (1.9L turbocharged Volkswagen Jetta TDI) diesel engine equipped with an OEM diesel oxidation catalyst and exhaust gas recirculation, mounted on an engine dynamometer. Acids measured included isocyanic, nitrous, nitric, propionic and sum of lactic and oxalic, as well as other unidentified compounds. Complimentary measurements of CO, CO2, Total Hydrocarbon (THC), and NOx, were also performed. Several engine modes (different engine rpm and torque outputs) at steady state were examined to determine their effect on acid emissions. Emission rates with respect to NOx and fuel based emission factors were determined. Measurements of HONO fuel emission factors agree well with real-world measurements within a traffic tunnel.1 The first estimate of isocyanic acid emission factors from a diesel engine is reported, and suggests that the emission of this highly toxic compound in diesel exhaust should not be ignored. 1. Kurtenbach, R., Becker, K. H., Gomes, J. A. G., Kleffmann, J.,Lorzer, J. C., Spittler, M., Wiesen, P., Ackermann, R., Geyer, A.,and Platt, U.: Investigations of emissions and heterogeneous formation of HONO in a road traffic tunnel, Atmos. Environ., 35, 3385-3394, doi:10.1016/S1352-2310(01)00138-8, 2001.

  13. Photocatalytic Iron Oxide Coatings Produced by Thermal Spraying Process

    NASA Astrophysics Data System (ADS)

    Navidpour, A. H.; Salehi, M.; Amirnasr, M.; Salimijazi, H. R.; Azarpour Siahkali, M.; Kalantari, Y.; Mohammadnezhad, M.

    2015-12-01

    Recently, hematite coatings with semiconductor properties have received attention for photocatalytic applications. In this study, plasma and flame spraying techniques were used for hematite deposition on 316 stainless steel plates. X-ray diffraction was used for phase composition analysis, and methylene blue was used as an organic pollutant to evaluate the photocatalytic activity of thermally sprayed coatings. The results showed that all these coatings could act under visible-light irradiation but the one deposited by flame spraying at 20 cm stand-off distance showed the highest photocatalytic activity. The results showed that wavelength of the light source and pH of the solution affected the photocatalytic activity significantly. It was also shown that thermally sprayed iron oxide coatings could have a high photo-absorption ability, which could positively affect the photocatalytic activity.

  14. Phototransformation of polychlorinated aromatics in gas phase and on aerosol

    NASA Astrophysics Data System (ADS)

    Zhang, Xinzhong

    1999-12-01

    A number of polychlorinated aromatics have been shown to pose health risks even at very low concentration levels. However, routes of introduction of these toxic congeners into the environment remain unclear. It is speculated that some of the toxic congeners may evolve, in part, from transformation of other less toxic congeners. The most likely route for these transformations is photolysis during atmospheric transport. An investigation of this phenomenon was undertaken in this study, and phototransformation of selected polychlorinated aromatics, representing the compound of environmental concern, such as PCDDs, PCDFs and PCBs, in gas phase were examined. The study involved monitoring the effect of various atmospheres on phototransformation mechanism and kinetics. The experimental setup consisted of the photoreactor coupled to a vapor generator, a particle generator, an electrostatic classifier, and a particle counter. This arrangement permitted introduction of contaminants at known concentrations in vapor or aerosol form. The contaminants were irradiated for varied periods and the disappearance kinetics was studied as a function of irradiation time. The correlation between congeners and the photodegradation pathway was also investigated. The first order kinetic constants and the quantum yields were measured. The experimental results showed that the vapor phase phototransformation rates are affected by the atmospheric parameters, e.g., phototransformation rates are significantly enhanced in the presence of oxygen. In general, less chlorinated compounds decomposed faster than higher chlorinated ones. The reductive dechlorination was evidenced through the formation of products with less chlorine substitution. The presence of hydrogen donors significantly increased the yield of the reductive dechlorination products. The oxygen dominated the phototransformation rates by the mechanisms other than reductive dechlorination. The phototransformation rates of the PCDDs

  15. Synergistic manipulation of micro-nanostructures and composition: anatase/rutile mixed-phase TiO2 hollow micro-nanospheres with hierarchical mesopores for photovoltaic and photocatalytic applications

    NASA Astrophysics Data System (ADS)

    Zhu, Qing; Qian, Jieshu; Pan, Hao; Tu, Luo; Zhou, Xingfu

    2011-09-01

    The construction of nanocrystals with controllable composition and desirable micro-nanostructures is a well-known challenge. A combination of favorable composition and optimized micro-nanostructures can enhance the performance of a material significantly. Using TiO2 as an example, we demonstrate here a facile approach to prepare anatase/rutile mixed-phase TiO2 hollow micro-nanospheres with hierarchical mesopores. Our strategy relies on polymer-assisted assembly of ~ 5 nm nano-building blocks into three-dimensional hierarchical hollow micro-nanospheres in a mixed alcohol-water solution. This superior micro-nanostructure endows the sample with hierarchical mesopores and a high surface area of 106 m2 g - 1. We also show that, due to the synergetic effects of the mixed-phase composition and the micro-nanostructures, the sample exhibited significantly improved photovoltaic performance and similar photocatalytic performance compared with the commercial Degussa P25. These results suggested that our sample has great potential for future photovoltaic and photocatalytic applications.

  16. A chamber study on the reactions of O3, NO, NO2 and selected VOCs with a photocatalytically active cementitious coating material.

    PubMed

    Mothes, F; Böge, O; Herrmann, H

    2016-08-01

    Chamber studies were performed to investigate the efficiency of a photocatalytically active cementitious coating material to depollute contaminated air. The results showed a photocatalytic effect on ozone (O3), proven by an increase of the geometric uptake coefficient from 5.2 × 10(-6) for the inactive to 7.7 × 10(-6) for the active material under irradiation. Measured first-order rate constants for nitrogen oxides (NOx) under irradiation are in the range of 2.6-5.9 × 10(-4) s(-1), which is significantly higher compared to the inactive material (7.3-9.7 × 10(-5) s(-1)) demonstrating the photocatalytic effect. However, no significant photocatalytic degradation was observed for the studied volatile organic compounds (VOCs) toluene and isoprene resulting in only an upper limit uptake coefficient of 5.0 × 10(-7) for both VOCs. In all experiments using the photocatalytically active material, a clear formation of small carbonyl (C1-C5) gas phase compounds was identified which is suggested to result from the photocatalytic degradation of organic additives. In contrast to the uptake observed for pure O3, during the experiments with NOx (≥50 % relative humidity), a clear photocatalytic formation of O3 was observed. For the material investigated, an empirically derived overall zero-order rate constant of k 0 (O3) ≈ 5 × 10(7) molecules cm(-3) s(-1) was determined. The results demonstrate the necessity of detailed studies of heterogeneous reactions on such surfaces under more complex simulated atmospheric conditions as enabled by simulation chambers. PMID:27102618

  17. Visible and ultraviolet spectroscopy of gas phase rhodamine 575 cations.

    PubMed

    Daly, Steven; Kulesza, Alexander; Knight, Geoffrey; MacAleese, Luke; Antoine, Rodolphe; Dugourd, Philippe

    2015-06-01

    The visible and ultraviolet spectroscopy of gas phase rhodamine 575 cations has been studied experimentally by action-spectroscopy in a modified linear ion trap between 220 and 590 nm and by time-dependent density functional theory (TDDFT) calculations. Three bands are observed that can be assigned to the electronic transitions S0 → S1, S0 → S3, and S0 → (S8,S9) according to the theoretical prediction. While the agreement between theory and experiment is excellent for the S3 and S8/S9 transitions, a large shift in the value of the calculated S1 transition energy is observed. A theoretical analysis of thermochromism, potential vibronic effects, and-qualitatively-electron correlation revealed it is mainly the latter that is responsible for the failure of TDDFT to accurately reproduce the S1 transition energy, and that a significant thermochromic shift is also present. Finally, we investigated the nature of the excited states by analyzing the excitations and discussed their different fragmentation behavior. We hypothesize that different contributions of local versus charge transfer excitations are responsible for 1-photon versus 2-photon fragmentation observed experimentally. PMID:25961329

  18. Gas-phase electronic spectrum of the indole radical cation

    NASA Astrophysics Data System (ADS)

    Chalyavi, N.; Catani, K. J.; Sanelli, J. A.; Dryza, V.; Bieske, E. J.

    2015-08-01

    The visible and near-UV electronic spectrum of the indole radical cation is measured in the gas phase by photodissociation of indole+-Ar and indole+-He complexes in a tandem mass spectrometer. A series of resolved vibronic transitions extending from 610 to 460 nm are assigned to the D2 ← D0 band system, while weak transitions between 390 and 360 nm are assigned to the D3 ← D0 system, and a stronger, broad, unresolved absorption between 350 and 300 nm is attributed to the D4 ← D0 system. Time-dependent density functional theory calculations are used to assign vibronic structure of the D2 ← D0 band system, and show that the main active vibrational modes correspond to in-plane ring deformations. The strongest D2 ← D0 vibronic transitions of indole+-He do not correspond with any catalogued diffuse interstellar bands, even considering band displacements of up to 50 cm-1possibly caused by the attached He atom.

  19. Surface plasmon sensing of gas phase contaminants using optical fiber.

    SciTech Connect

    Thornberg, Steven Michael; White, Michael I.; Rumpf, Arthur Norman; Pfeifer, Kent Bryant

    2009-10-01

    Fiber-optic gas phase surface plasmon resonance (SPR) detection of several contaminant gases of interest to state-of-health monitoring in high-consequence sealed systems has been demonstrated. These contaminant gases include H{sub 2}, H{sub 2}S, and moisture using a single-ended optical fiber mode. Data demonstrate that results can be obtained and sensitivity is adequate in a dosimetric mode that allows periodic monitoring of system atmospheres. Modeling studies were performed to direct the design of the sensor probe for optimized dimensions and to allow simultaneous monitoring of several constituents with a single sensor fiber. Testing of the system demonstrates the ability to detect 70mTorr partial pressures of H{sub 2} using this technique and <280 {micro}Torr partial pressures of H{sub 2}S. In addition, a multiple sensor fiber has been demonstrated that allows a single fiber to measure H{sub 2}, H{sub 2}S, and H{sub 2}O without changing the fiber or the analytical system.

  20. Gas-phase Chemistry of the Cyanate Ion, OCN-

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  1. Relating gas phase to solution conformations: Lessons from disordered proteins

    PubMed Central

    Beveridge, Rebecca; Phillips, Ashley S.; Denbigh, Laetitia; Saleem, Hassan M.; MacPhee, Cait E.

    2015-01-01

    In recent years both mass spectrometry (MS) and ion mobility mass spectrometry (IM‐MS) have been developed as techniques with which to study proteins that lack a fixed tertiary structure but may contain regions that form secondary structure elements transiently, namely intrinsically disordered proteins (IDPs). IM‐MS is a suitable method for the study of IDPs which provides an insight to conformations that are present in solution, potentially enabling the analysis of lowly populated structural forms. Here, we describe the IM‐MS data of two IDPs; α‐Synuclein (α‐Syn) which is implicated in Parkinson's disease, and Apolipoprotein C‐II (ApoC‐II) which is involved in cardiovascular diseases. We report an apparent discrepancy in the way that ApoC‐II behaves in the gas phase. While most IDPs, including α‐Syn, present in many charge states and a wide range of rotationally averaged collision cross sections (CCSs), ApoC‐II presents in just four charge states and a very narrow range of CCSs, independent of solution conditions. Here, we compare MS and IM‐MS data of both proteins, and rationalise the differences between the proteins in terms of different ionisation processes which they may adhere to. PMID:25920945

  2. Relating gas phase to solution conformations: Lessons from disordered proteins.

    PubMed

    Beveridge, Rebecca; Phillips, Ashley S; Denbigh, Laetitia; Saleem, Hassan M; MacPhee, Cait E; Barran, Perdita E

    2015-08-01

    In recent years both mass spectrometry (MS) and ion mobility mass spectrometry (IM-MS) have been developed as techniques with which to study proteins that lack a fixed tertiary structure but may contain regions that form secondary structure elements transiently, namely intrinsically disordered proteins (IDPs). IM-MS is a suitable method for the study of IDPs which provides an insight to conformations that are present in solution, potentially enabling the analysis of lowly populated structural forms. Here, we describe the IM-MS data of two IDPs; α-Synuclein (α-Syn) which is implicated in Parkinson's disease, and Apolipoprotein C-II (ApoC-II) which is involved in cardiovascular diseases. We report an apparent discrepancy in the way that ApoC-II behaves in the gas phase. While most IDPs, including α-Syn, present in many charge states and a wide range of rotationally averaged collision cross sections (CCSs), ApoC-II presents in just four charge states and a very narrow range of CCSs, independent of solution conditions. Here, we compare MS and IM-MS data of both proteins, and rationalise the differences between the proteins in terms of different ionisation processes which they may adhere to. PMID:25920945

  3. Concurrence of aqueous and gas phase contamination of groundwater in the Wattenberg oil and gas field of northern Colorado.

    PubMed

    Li, Huishu; Son, Ji-Hee; Carlson, Kenneth H

    2016-01-01

    The potential impact of rapid development of unconventional oil and natural gas resources using hydraulic fracturing and horizontal drilling on regional groundwater quality has received significant attention. Major concerns are methane or oil/gas related hydrocarbon (such as TPHs, BTEX including benzene, toluene, ethybenzene and xylene) leaks into the aquifer due to the failure of casing and/or stray gas migration. Previously, we investigated the relationship between oil and gas activity and dissolved methane concentration in a drinking water aquifer with the major finding being the presence of thermogenic methane contamination, but did not find detectable concentrations of TPHs or BTEX. To understand if aqueous and gas phases from the producing formation were transported concurrently to drinking water aquifers without the presence of oil/gas related hydrocarbons, the ionic composition of three water groups was studied: (1) uncontaminated deep confined aquifer, (2) suspected contaminated groundwater - deep confined aquifer containing thermogenic methane, and (3) produced water from nearby oil and gas wells that would represent aqueous phase contaminants. On the basis of quantitative and spatial analysis, we identified that the "thermogenic methane contaminated" groundwater did not have similarities to produced water in terms of ionic character (e.g. Cl/TDS ratio), but rather to the "uncontaminated" groundwater. The analysis indicates that aquifer wells with demonstrated gas phase contamination have not been contacted by an aqueous phase from oil and gas operations according to the methodology we use in this study and the current groundwater quality data from COGCC. However, the research does not prove conclusively that this the case. The results may provide insight on contamination mechanisms since improperly sealed well casing may result in stray gas but not aqueous phase transport. PMID:26519629

  4. DEMONSTRATION OF FUEL CELLS TO RECOVER ENERGY FROM LANDFILL GAS: PHASE II. PRETREATMENT SYSTEM PERFORMANCE MEASUREMENT

    EPA Science Inventory

    The report describes-Phase II of a demonstration of the utilization of commercial phosphoric acid fuel cells to recover energy from landfill gas. his phase consisted primarily of the construction and testing of a Gas Pretreatment Unit (GPU) whose function is to remove those impur...

  5. Magnetic field dependence of the product yields of cycloheptanone photolysis in the dilute gas phase

    NASA Astrophysics Data System (ADS)

    Stich, E. M.; Baumeister, W. F.; Huber, J. Robert

    1984-07-01

    The product yields of the gas-phase photolysis of cycloheptanone were measured in magnetic fields up to 10 kG. The magnetic-field effect is explained in terms of the radical pair model. A reaction mechanism is proposed that explains the magnetic field dependence, pressure dependence, and excitation enegy dependence of the gas-phase photochemistry of cycloheptanone.

  6. DEMONSTRATION OF FUEL CELLS TO RECOVER ENERGY FROM LANDFILL GAS: PHASE II. PRETREATMENT SYSTEM PERFORMANCE MEASUREMENT

    EPA Science Inventory

    The report describes Phase II of a demonstration of the utilization of commercial phosphoric acid fuel cells to recover energy from landfill gas. This phase consisted primarily of the construction and testing of a Gas Pretreatment Unit (GPU) whose function is to remove those impu...

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

    EPA Science Inventory

    Gas Phase Selective Oxidation of Alcohols Using Light-Activated Titanium Dioxide and Molecular Oxygen

    Gas phase selective oxidations of various primary and secondary alcohols are studied in an indigenously built stainless steel up-flow photochemical reactor using ultravi...

  8. Synthesis of Metal Ion-Doped TiO2 Nanoparticles Using Two-Phase Method and Their Photocatalytic Activity Under Visible Light Irradiation.

    PubMed

    Nguyen, Duy-Trinh; Hong, Seong-Soo

    2016-02-01

    In this study, TiO2 and metal ion-doped TiO2 nanoparticles were successfully synthesized by solvothermal reaction of titanium butoxide precursor in the presence of oleic acid, oleylamine and vapor water and they were characterized by XRD, Raman, TEM and DRS. We also investigated the photocatalytic activity of these oxides for the decomposition of Rhodamine B. From XRD and Raman results, doping of the metal ion in the crystal lattice did not change the high crystallinity of the TiO2 structure, and all the metal ions were incorporated into the structures of titania as well as replaced titanium ion or located at interstitial site. The absorption band shifted to a higher wavelength on the metal ion-doped TiO2 samples compared to the pure TiO2 sample. The Ce ion- doped TiO2 catalysts showed the higher photocatalytic activity compared to the pure TiO2 and a commercial P-25 catalysts and 1% Ce-doped TiO2 showed the highest photocatalytic activity. PMID:27433699

  9. Gas-Phase Combustion Synthesis of Aluminum Nitride Powder

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  10. Gas phase selective hydrogenation over oxide supported Ni-Au.

    PubMed

    Cárdenas-Lizana, Fernando; Keane, Mark A

    2015-11-14

    The chemoselective continuous gas phase (T = 573 K; P = 1 atm) hydrogenation of nitroarenes (p-chloronitrobenzene (p-CNB) and m-dinitrobenzene (m-DNB)) has been investigated over a series of oxide (Al2O3 and TiO2) supported Au and Ni-Au (1 : 10 mol ratio; 0.1-1 mol% Au) catalysts. Monometallic supported Au with mean particle size 3-9 nm promoted exclusive formation of p-chloroaniline (p-CAN) and m-nitroaniline (m-NAN). Selective hydrogenation rate was higher over smaller Au particles and can be attributed to increased surface hydrogen (from TPD measurements) at higher metal dispersion. (S)TEM analysis has confirmed an equivalent metal particle size for the supported bimetallics at the same Au loading where TPR indicates Ni-Au interaction and EDX surface mapping established Ni in close proximity to Au on isolated nanoparticles with a composition (Au/Ni) close to the bulk value (= 10). Increased spillover hydrogen due to the incorporation of Ni in the bimetallics resulted in elevated -NO2 group reduction rate. Full selectivity to p-CAN was maintained over all the bimetallic catalysts. Conversion of m-DNB over the lower loaded Ni-Au/Al2O3 generated m-NAN as sole product. An increase in Ni content (0.01 → 0.1 mol%) or a switch from Al2O3 to TiO2 as support resulted in full -NO2 reduction (to m-phenylenediamine). Our results demonstrate the viability of Ni-promotion of Au in the continuous production of functionalised anilines. PMID:25752655

  11. Dissociative Attachment Reactions of Electrons with Gas Phase Superacids

    NASA Astrophysics Data System (ADS)

    Liu, Xifan

    Using the flowing afterglow Langmuir probe (FALP) technique, dissociative attachment coefficients beta for reactions of electrons with gas phase superacids HCo(PF_3)_4, HRh(PF _3)_4 and carbonyl hydride complexes HMn(CO)_5, HRe(CO) _5 have been determined under thermal conditions over the approximate temperature range 300~ 550 K. The superacids react relatively slowly (< 1/20 of beta_{rm max}) with free electrons in a thermal plasma, and the values of beta obtained this far do not show a correlation between acidity and beta. The pioneer researchers in this field had speculated that any superacid would be a rapid attacher of electrons; we found that this speculation is not true in general. The product distribution of electron attachment reaction to HCo(PF_3)_4 was found to be independent of temperature even though the beta (HCo(PF_3)_4 ) increases with temperature. This leads us to propose that the electron attachment process occurs well before the excited complex dissociates. In addition, the activation energy of HCo(PF_3)_4 for electron attachment has been derived from the Arrhenius plots. The carbonyl hydride complexes, HMn(CO) _5 and HRe(CO)_5, react relatively rapidly (>1/4 of beta_{rm max}) with free electrons in thermal plasma. This indicates that these reactions cannot be significantly endothermic. Observation of rapid attachment for these non-superacids shows that the Mn-CO and Re-CO bonds are weaker than the Mn-H and Re-H bonds, respectively. Comparisons between the carbonyl and trifluorophosphine cases implies that fast electron capture is related more to the CO ligand than to the transition -metal species.

  12. IV-VI semiconductor lasers for gas phase biomarker detection

    NASA Astrophysics Data System (ADS)

    McCann, Patrick; Namjou, Khosrow; Roller, Chad; McMillen, Gina; Kamat, Pratyuma

    2007-09-01

    A promising absorption spectroscopy application for mid-IR lasers is exhaled breath analysis where sensitive, selective, and speedy measurement of small gas phase biomarker molecules can be used to diagnose disease and monitor therapies. Many molecules such as nitric oxide, ethane, formaldehyde, acetaldehyde, acetone, carbonyl sulfide, and carbon disulfide have been connected to diseases or conditions such as asthma, oxidative stress, breast cancer, lung cancer, diabetes, organ transplant rejection, and schizophrenia. Measuring these and other, yet to be discovered, biomarker molecules in exhaled breath with mid-IR lasers offers great potential for improving health care since such tests are non-invasive, real-time, and do not require expensive consumables or chemical reagents. Motivated by these potential benefits, mid-IR laser spectrometers equipped with presently available cryogenically-cooled IV-VI lasers mounted in compact Stirling coolers have been developed for clinical research applications. This paper will begin with a description of the development of mid-IR laser instruments and their use in the largest known exhaled breath clinical study ever performed. It will then shift to a description of recent work on the development of new IV-VI semiconductor quantum well materials and laser fabrication methods that offer the promise of low power consumption (i.e. efficient) continuous wave emission at room temperature. Taken together, the demonstration of compelling clinical applications with large market opportunities and the clear identification of a viable pathway to develop low cost mid-IR laser instrumentation can create a renewed focus for future research and development efforts within the mid-IR materials and devices area.

  13. Gas-Phase Combustion Synthesis of Nonoxide Nanoparticles in Microgravity

    NASA Technical Reports Server (NTRS)

    Axelbaum, R. L.; Kumfer, B. M.; Sun, Z.; Chao, B. H.

    2001-01-01

    Gas-phase combustion synthesis is a promising process for creating nanoparticles for the growing nanostructure materials industry. The challenges that must be addressed are controlling particle size, preventing hard agglomerates, maintaining purity, and, if nonoxides are synthesized, protecting the particles from oxidation and/or hydrolysis during post-processing. Sodium-halide Flame Encapsulation (SFE) is a unique methodology for producing nonoxide nanoparticles that addresses these challenges. This flame synthesis process incorporates sodium and metal-halide chemistry, resulting in nanoparticles that are encapsulated in salt during the early stages of their growth in the flame. Salt encapsulation has been shown to allow control of particle size and morphology, while serving as an effective protective coating for preserving the purity of the core particles. Metals and compounds that have been produced using this technology include Al, W, Ti, TiB2, AlN, and composites of W-Ti and Al-AlN. Oxygen content in SFE synthesized nano- AlN has been measured by neutron activation analysis to be as low as 0.54wt.%, as compared to over 5wt.% for unprotected AlN of comparable size. The overall objective of this work is to study the SFE process and nano-encapsulation so that they can be used to produce novel and superior materials. SFE experiments in microgravity allow the study of flame and particle dynamics without the influence of buoyancy forces. Spherical sodium-halide flames are produced in microgravity by ejecting the halide from a spherical porous burner into a quiescent atmosphere of sodium vapor and argon. Experiments are performed in the 2.2 sec Drop Tower at the NASA-Glenn Research Center. Numerical models of the flame and particle dynamics were developed and are compared with the experimental results.

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

    SciTech Connect

    Dawley, M. Michele; Tanzer, Katrin; Denifl, Stephan E-mail: Sylwia.Ptasinska.1@nd.edu; Carmichael, Ian; Ptasińska, Sylwia E-mail: Sylwia.Ptasinska.1@nd.edu

    2015-06-07

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

  15. The Gas-Phase Deuterium Fractionation of Formaldehyde

    NASA Astrophysics Data System (ADS)

    Osamura, Yoshihiro; Roberts, Helen; Herbst, Eric

    2005-03-01

    The dominant mechanism for the deuteration of formaldehyde in the gas phase of low-temperature interstellar cloud cores occurs via reaction with the deuterating ions H2D+, HD+2, and D+3. Until now, it has been assumed that deuteration leads to an ion that, on recombination with electrons, can produce a deuterated neutral species with a statistical branching fraction. Quantum chemical calculations reported here, however, show an entirely different picture, in which the deuteration of formaldehyde leads to the molecular ion H2COD+, where the deuterium binds only on the oxygen side of the molecule. The structure is quite stable, while an alternative structure, H2DCO+, cannot be produced in a straightforward manner. Dissociative recombination of H2COD+ to reproduce a formaldehyde structure then removes the deuteration if the dissociation is direct, i.e., it occurs without change of structure. There are several possible indirect mechanisms by which dissociative recombination can lead to HDCO, however. For example, if the direct products are HCOD+H, it is possible that subsequent isomerization to HDCO can occur, although this involved process is unlikely. Another possibility is isomerization during the actual dissociation of the H2COD intermediate. Models of deuterium fractionation in which dissociative recombination is predominantly direct are presented, and it is found that the deuterium fractionation of formaldehyde to form both HDCO and D2CO can still occur via other mechanisms, although with less efficiency than previously obtained. If the dissociative recombination is half indirect, however, then we can recover the previously calculated efficiency.

  16. Laboratory Investigations of Titan Haze Formation: Characterization of Gas Phase and Particle Phase Nitrogen

    NASA Astrophysics Data System (ADS)

    Horst, Sarah; Yoon, Heidi; Li, Rui; deGouw, Joost; Tolbert, Margaret

    2014-11-01

    Prior to the arrival of the Cassini-Huygens spacecraft, aerosol production in Titan’s atmosphere was believed to begin in the stratosphere where chemical processes are predominantly initiated by far ultraviolet (FUV) radiation. However, the discovery of very heavy ions, coupled with Cassini Ultraviolet Imaging Spectrograph (UVIS) occultation measurements that show haze absorption up to 1000 km altitude (Liang et al., 2007), indicates that haze formation initiates in the thermosphere. The energy environment of the thermosphere is significantly different from the stratosphere; in particular there is a greater flux of extreme ultraviolet (EUV) photons and energetic particles available to initiate chemical reactions, including the destruction of N2, in the upper atmosphere. The discovery of previously unpredicted nitrogen species in measurements of Titan’s atmosphere by the Cassini Ion and Neutral Mass Spectrometer (INMS) indicates that nitrogen participates in the chemistry to a much greater extent than was appreciated before Cassini (Vuitton et al., 2007). Additionally, measurements obtained by the Aerosol Collector Pyrolyzer (ACP) carried by Huygens to Titan’s surface may indicate that Titan’s aerosols contain significant amounts of nitrogen (Israël et al., 2005, 2006). The degree of nitrogen incorporation in the haze particles is important for understanding the diversity of molecules that may be present in Titan’s atmosphere and on its surface. We have conducted a series of Titan atmosphere simulation experiments using either spark discharge (tesla coil) or FUV photons (deuterium lamp) to initiate chemistry in CH4/N2 gas mixtures ranging from 0.01% CH4/99.99% N2 to 10% CH4/90% N2. We obtained in situ measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) to measure the particle composition as a function of particle size and a proton-transfer ion-trap mass spectrometer (PIT-MS) to measure the composition of gas phase

  17. Capillary effects on gas hydrate three-phase stability in marine sediments

    NASA Astrophysics Data System (ADS)

    Liu, X.; Flemings, P. B.

    2013-12-01

    We study the three-phase (Liquid + Gas + Hydrate) stability of the methane hydrate system in marine sediments by considering the capillary effects on both hydrate and free gas phases. The aqueous CH4 solubilities required for forming hydrate (L+H) and free gas (L+G) in different pore sizes can be met in a three-phase zone. The top of the three-phase zone shifts upward in sediments as the water depth increases and the mean pore size decreases. The thickness of the three-phase zone increases as the pore size distribution widens. The top of the three-phase zone can either overlie the three-phase stability depth at deepwater Blake Ridge or underlie the three-phase stability depth at Hydrate Ridge in shallow water. Our model prediction is compatible with worldwide observations that the bottom-simulating reflector is systematically shifted upward relative to the bulk equilibrium depth as water depth (pressure) is increased. The gas hydrate and free gas saturations of the three-phase zone at Blake Ridge Comparison of the globally compiled BSR temperatures with the three-phase equilibrium curves for the systems of pure CH4 + 3.5 wt.% seawater (solid line) and pure CH4 + 2.0 wt.% seawater (dotted line). The discrepancies between the observed BSR temperature and the calculated three-phase temperature are systematically larger in deep water than in shallow water.

  18. The Relative Importance of Aqueous-Phase and Gas-Phase Phenol Oxidation as Sources of SOA (Invited)

    NASA Astrophysics Data System (ADS)

    Anastasio, C.; Smith, J.

    2010-12-01

    The oxidation of phenols is a source of secondary organic aerosol (SOA) in the gas phase as well as in aqueous phases (e.g., cloud and fog drops and water-containing aerosol particles). The relative importance of the gas- and aqueous-phase pathways depends largely on three factors: (1) the partitioning of phenols between the gaseous and condensed phases, (2) the rates of reaction in each phase, and (3) the yields of SOA in each phase. Our goal in this work is to determine the relative importance of these two pathways as sources of SOA. Using previously published rate constants, as well as newly determined kinetics and SOA yield data in the aqueous phase, we find that in a cloudy atmosphere both aqueous- and gas-phase sinks are significant for phenols with high vapor pressures (e.g., phenol itself), but that aqueous-phase sinks can dominate for phenols with lower vapor pressures (e.g., phenols with multiple hydroxy or methoxy substituents). In regions with wood combustion (a major source of phenols), our calculations indicate that destruction of phenols within wood smoke particles is very important and that reaction with particulate triplet excited states is a major sink.

  19. CO2 Capture from Flue Gas by Phase Transitional Absorption

    SciTech Connect

    Liang Hu

    2009-06-30

    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.

  20. Effect of annealing treatment on the photocatalytic activity of TiO2 thin films deposited by dc reactive magnetron sputtering

    NASA Astrophysics Data System (ADS)

    Arias, L. M. Franco; Arias Duran, A.; Cardona, D.; Camps, E.; Gómez, M. E.; Zambrano, G.

    2015-07-01

    Titanium dioxide (TiO2) thin films have been deposited by DC reactive magnetron sputtering on silicon and quartz substrates with different Ar/O2 ratios in the gas mixture. Substrate temperature was kept constant at 400 °C during the deposition process, and the TiO2 thin films were later annealed at 700 °C for 3 h. The effect of the Ar/O2 ratio in the gas flow and the annealing treatment on the phase composition, deposition rate, crystallinity, surface morphology and the resulting photocatalytic properties were investigated. For photocatalytic measurements, the variation of the concentration of the methylene blue (MB) dye under UV irradiation was followed by a change in the intensity of the characteristic MB band in the UV- Vis transmittance spectra. We report here that the as-grown TiO2 films showed only the anatase phase, whereas after annealing, the samples exhibited both the anatase and rutile phases in proportions that varied with the Ar/O2 ratio in the mixture of gases used during growth. In particular, the annealed TiO2 thin film deposited at a 50/50 ratio of Ar/O2, composed of both anatase (80%) and rutile phases (20%), exhibited the highest photocatalytic activity (30% of MB degradation) compared with the samples without annealing and composed of only the anatase phase.

  1. Condensed-phase versus gas-phase ozonolysis of catechol: A combined experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Barnum, Timothy J.; Medeiros, Nicholas; Hinrichs, Ryan Z.

    2012-08-01

    Anthropogenic emissions of volatile aromatic compounds contribute to the formation of secondary organic aerosols (SOA), especially in urban environments. Aromatic SOA precursors typically require oxidation by hydroxyl radicals, although recent work suggests that ozonolysis of 1,2-benzenediols produces SOA in high yields. We employed attenuated total reflectance and transmission infrared spectroscopy to investigate the heterogeneous ozonolysis of catechol thin films. Formation of the dominant condensed-phase product muconic acid was highly dependent on relative humidity (RH) with few products detected below 40% RH and a maximum reactive uptake coefficient of γ = (5.6 ± 0.5) × 10-5 measured at 81.2% RH. We also performed quantum chemical calculations mapping out several reaction pathways for the homogeneous ozonolysis of gaseous catechol. 1,3-cycloaddition transition states were rate limiting with the most favorable activation energies at 45.4 and 47.1 kJ mol-1 [CCSD(T)/6-311++G(d,p)] corresponding to addition across and adjacent to the diol Cdbnd C, respectively. Gas-phase rate constants, calculated using transition state theory, were six orders of magnitude slower than experimental values. In contrast, a calculated activation energy was lower for the ozonolysis of a catechol•H2O complex, which serves as a first-approximation for modeling the ozonolysis of condensed-phase catechol. These combined results suggests that homogeneous ozonolysis of catechol may not be important for the formation of secondary organic aerosols but that ozonolysis of surface-adsorbed catechol may contribute to SOA growth.

  2. Integrated photocatalytic filtration array for indoor air quality control.

    PubMed

    Denny, Frans; Permana, Eric; Scott, Jason; Wang, Jing; Pui, David Y H; Amal, Rose

    2010-07-15

    Photocatalytic and filtration technologies were integrated to develop a hybrid system capable of removing and oxidizing organic pollutants from an air stream. A fluidized bed aerosol generator (FBAG) was adapted to prepare TiO(2)-loaded ventilation filters for the photodegradation of gas phase ethanol. Compared to a manually loaded filter, the ethanol photodegradation rate constant for the FBAG coated filter increased by 361%. Additionally, the presence of the photogenerated intermediate product, acetaldehyde, was reduced and the time for mineralization to CO(2) was accelerated. These improvements were attributed to the FBAG system providing a more uniform distribution of TiO(2) particles across the filter surface leading to greater accessibility by the UV light. A dual-UV-lamp system, as opposed to a single-lamp system, enhanced photocatalytic filter performance demonstrating the importance of high light irradiance and light distribution across the filter surface. Substituting the blacklight blue lamps with a UV-light-emitting-diode (UV-LED) array led to further improvement as well as suppressed the electrical energy per order (EE/O) by a factor of 6. These improvements derived from the more uniform distribution of light irradiance as well as the higher efficiency of UV-LEDs in converting electrical energy to photons. PMID:20550189

  3. Three-phase measurements of oil and gas trapping in sand packs

    NASA Astrophysics Data System (ADS)

    Al Mansoori, Saleh K.; Iglauer, Stefan; Pentland, Christopher H.; Blunt, Martin J.

    2009-10-01

    We measure the trapped saturations of oil and gas as a function of initial saturation in water-wet sand packs. We start with a water-saturated column and inject octane (oil), while water and oil are produced from the bottom. Once water production has ceased, air (gas) then enters from the top, allowing oil and gas to drain under gravity for different times. Finally water is then injected from the bottom to trap both oil and gas. The columns are sliced and the fluids analyzed using gas chromatography. We find that for high initial gas saturations more gas can be trapped in the presence of oil than in a two-phase (gas/water) system. The residual gas saturation can be over 20% compared to 14% in two-phase flow [Al Mansoori SK, Iglauer S, Pentland CH, Bijeljic B, Blunt MJ. Measurements of non-wetting phase trapping applied to carbon dioxide storage. Energy Procedia 2009;1(1):3173-80]. This is unlike previous measurements on consolidated media, where the trapped gas saturation is either similar or lower to that reached in an equivalent two-phase experiment. For lower initial gas saturation, the amount of trapping follows the initial-residual trend seen in two-phase experiments. The amount of oil trapped is insensitive to initial gas saturation or the amount of gas that is trapped, again in contrast to measurements on consolidated media. More oil is trapped than would be predicted from an equivalent two-phase (oil/water) system, although the trapped saturation is never larger than the maximum reached in two-phase flow (around 11%) [Pentland CH, Al Mansoori SK, Iglauer S, Bijeljic B, Blunt MJ. Measurement of non-wetting phase trapping in sand packs. In: SPE 115697, proceedings of the SPE annual technical conference and exhibition, Denver, Colorado, USA; 21-24 September 2008]. These initially surprising results are explained in the context of oil layer stability and the competition between snap-off and piston-like advance. In two-phase systems, displacement is principally

  4. Photocatalytic reduction of CO2 over Ag/TiO2 nanocomposites prepared with a simple and rapid silver mirror method

    NASA Astrophysics Data System (ADS)

    Yu, Bingcheng; Zhou, Yong; Li, Peng; Tu, Wenguang; Li, Ping; Tang, Lanqin; Ye, Jinhua; Zou, Zhigang

    2016-06-01

    The photocatalytic reduction of CO2 over Ag/TiO2 composites prepared with a simple silver mirror reaction method was investigated under UV-visible irradiation in both gas-phase (CO2 + water vapor) and aqueous solution (CO2-saturated NaHCO3 solution) systems. The as-prepared Ag/TiO2 nanocomposite exhibits efficient photocatalytic activity due to the surface plasmonic resonance and electron sink effect of the Ag component, which was found to be closely related to the size and loading amount of Ag. The rapid silver method is effective at curbing the size of Ag, so photocatalytic activity can be improved. Diverse organic chemical products were detected, including mainly methane and methanol as well as a small amount of C2 and C3 species such as acetaldehyde and acetone. Possible photocatalytic mechanisms were proposed. This artificial photosynthesis process may give a prosperous route to the removal of CO2 while simultaneously converting CO2 to valuable fuels based on highly efficient photocatalysts.The photocatalytic reduction of CO2 over Ag/TiO2 composites prepared with a simple silver mirror reaction method was investigated under UV-visible irradiation in both gas-phase (CO2 + water vapor) and aqueous solution (CO2-saturated NaHCO3 solution) systems. The as-prepared Ag/TiO2 nanocomposite exhibits efficient photocatalytic activity due to the surface plasmonic resonance and electron sink effect of the Ag component, which was found to be closely related to the size and loading amount of Ag. The rapid silver method is effective at curbing the size of Ag, so photocatalytic activity can be improved. Diverse organic chemical products were detected, including mainly methane and methanol as well as a small amount of C2 and C3 species such as acetaldehyde and acetone. Possible photocatalytic mechanisms were proposed. This artificial photosynthesis process may give a prosperous route to the removal of CO2 while simultaneously converting CO2 to valuable fuels based on highly

  5. FLUE GAS DESULFURIZATION PILOT STUDY. PHASE II. APPLICABILITY STUDY

    EPA Science Inventory

    The North Atlantic Treaty Organization Committee on the Challenges of Modern Society (NATO-CCMS) Flue Gas Desulfurization (FGD) Study Group prepared status reports on 12 FGD processes. Results of this work are summarized in NATO Report No. 95 titled 'Flue Gas Desulfurization Pilo...

  6. Dissolved gas transport in the presence of a trapped gas phase: Experimental evaluation of a two-dimensional kinetic model

    SciTech Connect

    Donaldson, J.H.; Istok, J.D.; O`Reilly, K.T.

    1998-01-01

    Quantitative information on dissolved gas transport in ground water aquifers is needed for a variety of site characterization and remedial design applications. The objective of this study was to gain further understanding of dissolved gas transport in the presence of trapped gas in the pore space of an otherwise water saturated porous medium, using a combination of laboratory experiments and numerical modeling. Transport experiments were conducted in a large-scale laboratory physical aquifer model containing a homogeneous sandpack. Tracer (Br{sup {minus}}) and dissolved gas (O{sub 2} or H{sub 2}) plumes were created using a two-well injection/extraction scheme and then were allowed to drift in a uniform flow field. Plume locations and shapes were monitored by measuring tracer and dissolved gas concentrations as a function of position within the sandpack and time. In all experiments, partitioning of the dissolved gases between the mobile ground water and stationary trapped gas phases resulted in substantial retardation and tailing of the dissolved O{sub 2} and H{sub 2} plumes relative to the Br{sup {minus}} plumes. Most observed plume features could be reproduced in simulations performed with a numerical model that combined the advection-dispersion equation with diffusion controlled mass transfer of dissolved gas between the mobile aqueous and stationary trapped gas phases. Fitted values of the volumetric trapped gas content and mass transfer coefficient ranged from 0.04 to 0.08 and from 10{sup {minus}6} to 10{sup {minus}5} sec{sup {minus}1}, respectively. Sensitivity analyses were used to examine how systematic variations in these parameters would be expected to affect dissolved gas transport under a range of potential field conditions. The experimental and modeling results indicate that diffusion controlled mass transfer should be considered when predicting dissolved gas transport in ground water aquifers in the presence of trapped gas.

  7. [Characteristics of water-gas two-phase CO2 transport in unsaturated zone].

    PubMed

    Yu, Yanxin; Chen, Jiajun; Wang, Jinsheng; Yun, Ying; Li, Shushen; Wang, Zhiming

    2003-07-01

    The migration of CO2 in soil was simulated through use of soil column, especially the transformation of CO2 between water and gas phases at wetting front was studied. The soil column in the test was 1 m long and the concentration of CO2 solution was 748 mg/L. Through analysis, it was shown that CO2 migration in water phase was governed by advection, dispersion, reaction and mass transfer between water and gas phases, that in gas phase by advection, dispersion, mass transfer between two phases. Sampling method under dynamic condition of two phase flow in soil column was approached and mass transfer coefficient from water phase to gas phase was determined as 0.00061. This showed that there was certain mass transformation of CO2 from water phase to gas phase and yet it was not so significant. This study can provide the quantitative scientific bases for safety assessment of geological disposal of low and intermediate level radioactive waste and environmental impact assessment of solid waste disposal by landfilling. PMID:14551970

  8. A new method for measurement of gas-phase ammonia and amines in air

    NASA Astrophysics Data System (ADS)

    Dawson, M. L.; Gomez, A.; Arquero, K. D.; Perraud, V. M.; Finlayson-Pitts, B. J.

    2013-12-01

    Accurately predicting particle formation and growth from gas phase precursors is an essential component of modeling the impact of particulate matter on human health, visibility and climate. While the reactions of ammonia with nitric and sulfuric acids to form particulate nitrate and sulfate particles is well known, it has been recently recognized that gas-phase amines, even at low ppb levels, significantly enhance particle formation from common atmospheric acids. As a result, accurate data on the sources, sinks and typical background concentrations of gas-phase amines, are crucial to predicting new particle formation in the atmosphere. However, gas-phase amines are notoriously difficult to measure, as they have a tendency to stick to surfaces, including sampling lines and inlets. In addition, background amine concentrations in the atmosphere are typically a few ppb or lower, requiring low detection limits for ambient sampling techniques. Here we report the development of a simple, reliable method for detection of gas-phase amines at atmospherically relevant concentrations using collection on a cation exchange sorbent followed by in-line extraction and ion chromatography. Gas-phase standards of several amines and ammonia are used to characterize the technique and results from ambient samples in an agricultural area are presented. The application of this technique to field measurements as well as to laboratory measurements of new particle formation from gas-phase ammonia and amines are discussed.

  9. Gas-phase lithium cation affinity of glycine.

    PubMed

    Bourcier, Sophie; Chiaa, Ru Xuan; Mimbong, Rosa Ngo Biboum; Bouchoux, Guy

    2015-01-01

    The gas-phase lithium cation binding thermochemistry of glycine has been determined theoretically by quantum chemical calculations at the G4 level and experimentally by the extended kinetic method using electrospray ionization quadrupole time-of-flight tandem mass spectrometry. The lithium cation affinity of glycine, ∆(Li)H°(298)(GLY), i.e. the∆(Li)H°(298) of the reaction GlyLi(+)→ Gly + Li(+)) given by the G4 method is equal to 241.4 kJ.mol(-1) if only the most stable conformer of glycine is considered or to 242.3 kJ.mol(-1) if the 298K equilibrium mixture of neutral conformers is included in the calculation. The ∆(Li)H°(298)(GLY) deduced from the extended kinetic method is obviously dependent on the choice of the Li(+) affinity scale, thus∆(Li)H°(298)(GLY) is equal to 228.7±0.9(2.0) kJ.mol(- 1) if anchored to the recently re-evaluated lithium cation affinity scale but shifted to 235.4±1.0 kJ.mol(-1) if G4 computed lithium cation affinities of the reference molecules is used. This difference of 6.3 kJ.mol(-1) may originate from a compression of the experimental lithium affinity scale in the high ∆(Li)H°(298) region. The entropy change associated with the reaction GlyLi(+)→Gly + Li(+) reveals a gain of approximately 15 J.mol(-) 1.K(-1) with respect to monodentate Li(+) acceptors. The origin of this excess entropy is attributed to the bidentate interaction between the Li(+) cation and both the carbonyl oxygen and the nitrogen atoms of glycine. The computed G4 Gibbs free energy,∆(Li)G°(298)(GLY) is equal to 205.3 kJ.mol(-1), a similar result, 201.0±3.4 kJ.mol(-1), is obtained from the experiment if the∆(Li)G°(298) of the reference molecules is anchored on the G4 results. PMID:26307695

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

    NASA Astrophysics Data System (ADS)

    Hack, W.

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

  11. The Noble Gas Record of Gas-Water Phase Interaction in the Tight-Gas-Sand Reservoirs of the Rocky Mountains

    NASA Astrophysics Data System (ADS)

    Ballentine, C. J.; Zhou, Z.; Harris, N. B.

    2015-12-01

    The mass of hydrocarbons that have migrated through tight-gas-sandstone systems before the permeability reduces to trap the hydrocarbon gases provides critical information in the hydrocarbon potential analysis of a basin. The noble gas content (Ne, Ar, Kr, Xe) of the groundwater has a unique isotopic and elemental composition. As gas migrates through the water column, the groundwater-derived noble gases partition into the hydrocarbon phase. Determination of the noble gases in the produced hydrocarbon phase then provides a record of the type of interaction (simple phase equilibrium or open system Rayleigh fractionation). The tight-gas-sand reservoirs of the Rocky Mountains represent one of the most significant gas resources in the United States. The producing reservoirs are generally developed in low permeability (averaging <0.1mD) Upper Cretaceous fluvial to marginal marine sandstones and commonly form isolated overpressured reservoir bodies encased in even lower permeability muddy sediments. We present noble gas data from producing fields in the Greater Green River Basin, Wyoming; the the Piceance Basin, Colorado; and in the Uinta Basin, Utah. The data is consistent from all three basins. We show how in each basin the noble gases record open system gas migration through a water column at maximum basin burial. The data within an open system model indicates that the gas now in-place represents the last ~10% of hydrocarbon gas to have passed through the water column, most likely prior to permeability closedown.

  12. Enhancement of gas-phase diffusion in the presence of liquid

    NASA Astrophysics Data System (ADS)

    Webb, S.; Angert, A.

    2003-04-01

    Gas diffusion in porous media occurs in both the gas and liquid phases. In many instances, gas diffusion in the liquid phase is ignored. However, under many conditions, gas diffusion in the liquid phase may be more important than gas diffusion in the gas phase. Two different cases will be examined in this work. The first case is a continuous liquid path between the gas concentrations of interest modeled after Jury et al. (1984). The second case is the situation at low liquid saturation where liquid islands exist. For the first case, Jury's model can be rewritten as a ratio of the total gas diffusion in the gas and liquid phases to that just in the gas phase. The liquid diffusion coefficient is approximately 10-4 times the gas diffusion coefficient consistent with Jury et al. (1984). The ratio of total diffusion to gas-phase diffusion is then only a function of Henry's constant and the liquid saturation. For higher values of Henry's constant, such as for CO2 and O2, the effect of diffusion in the liquid phase is small except at high liquid saturations. For small values of Henry's constant, such as for some VOCs and explosive compounds, diffusion in the liquid phase dominates for low and moderate liquid saturation values. The second case is the enhancement of diffusion caused by liquid islands at low liquid saturation. Enhanced vapor diffusion across liquid islands has been observed and modeled by Webb and Ho (1999), where condensation and evaporation occur on opposite ends of the liquid island. Vapor diffusion enhancement of up to a factor of 10 has been observed. Similarly, gas can diffuse through the liquid island. For high values of Henry's constant, gas diffusion through liquid islands is negligible and can be ignored. For small values of Henry's constant, diffusion through liquid islands may be much greater than diffusion through gas, so the rate is enhanced. The work was sponsored by the Geneva International Center for Humanitarian Demining (GICHD) under the

  13. The gas-phase thermal chemistry of tetralin and related model systems

    SciTech Connect

    Malandra, J.

    1993-05-01

    The thesis is divided into 5 papers: gas-phase thermal decomposition of tetralin; flash vacuum pyrolysis of 3-benzocycloheptenone and 1,3, 4,5-tetrahydro-2-benzothiepin-2,2-dioxide (model systems for gas-phase pyrolysis of tetralin); high-temperature gas-phase reactions of o-allylbenzyl radicals generated by flash vacuum pyrolysis of is(o-allylbenzyl) oxalate; flash vacuum pyrolysis of 1,4-diphenylbutane; and flash vacuum pyrolysis of o-allyltoluene, o-(3-butenyl)toluene and o-(pentenyl)toluene were also used.

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

    DOEpatents

    Stephens, H.P.

    1986-06-05

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

  15. The gas-phase metallicity of central and satellite galaxies in the Sloan Digital Sky Survey

    NASA Astrophysics Data System (ADS)

    Pasquali, Anna; Gallazzi, Anna; van den Bosch, Frank C.

    2012-09-01

    We exploit the galaxy groups catalogue of Yang et al. and the galaxy properties measured in the Sloan Digital Sky Survey Data Releases 4 and 7 to study how the gas-phase metallicities of star-forming galaxies depend on environment. We find that satellite and central galaxies follow a qualitatively similar stellar mass (M★)-gas-phase metallicity relation, whereby their gas-phase metallicity increases with M★. Satellites, though, have higher gas-phase metallicities than equally massive centrals, and this difference increases with decreasing stellar mass. We find a maximum offset of 0.06 dex at log(M★/h-2 M⊙) ≃ 8.25. At fixed halo mass, centrals are more metal rich than satellites by ˜0.5 dex on average. This is simply due to the fact that, by definition, centrals are the most massive galaxies in their groups, and the fact that gas-phase metallicity increases with stellar mass. More interestingly, we also find that the gas-phase metallicity of satellites increases with halo mass (Mh) at fixed stellar mass. This increment is more pronounced for less massive galaxies, and, at M★ ≃ 109 h-2 M⊙, corresponds to ˜0.15 dex across the range 11 < log (Mh/h-1 M⊙) < 14. We also show that low-mass satellite galaxies have higher gas-phase metallicities than central galaxies of the same stellar metallicity. This difference becomes negligible for more massive galaxies of roughly solar metallicity. We demonstrate that the observed differences in gas-phase metallicity between centrals and satellites at fixed M★ are not a consequence of stellar mass stripping (advocated by Pasquali et al. in order to explain similar differences but in stellar metallicity), nor to the past star formation history of these galaxies as quantified by their surface mass density or gas mass fraction. Rather, we argue that these trends probably originate from a combination of three environmental effects: (i) strangulation, which prevents satellite galaxies from accreting new, low

  16. An investigation into the flow behavior of a single phase gas system and a two phase gas/liquid system in normal gravity with nonuniform heating from above

    NASA Technical Reports Server (NTRS)

    Disimile, Peter J.; Heist, Timothy J.

    1990-01-01

    The fluid behavior in normal gravity of a single phase gas system and a two phase gas/liquid system in an enclosed circular cylinder heated suddenly and nonuniformly from above was investigated. Flow visualization was used to obtain qualitative data on both systems. The use of thermochromatic liquid crystal particles as liquid phase flow tracers was evaluated as a possible means of simultaneously gathering both flow pattern and temperature gradient data for the two phase system. The results of the flow visualization experiments performed on both systems can be used to gain a better understanding of the behavior of such systems in a reduced gravity environment and aid in the verification of a numerical model of the system.

  17. Phase-field simulation of gas bubble growth and flow in a Hele-Shaw cell

    NASA Astrophysics Data System (ADS)

    Sun, Ying

    2005-11-01

    A diffuse interface model has been developed for gas bubble growth and dynamics in a supersaturated liquid. The liquid becomes supersaturated in the gas species because of a drop in the pressure or temperature. The bubbles grow by gas diffusion in the liquid towards the bubble interfaces. During bubble growth, flows are induced by the large density contrast between the phases. The bubbles coarsen due to surface tension effects. The process widely exists in biological systems, materials processing, oil recovery, and other applications. The flows in the gas and liquid phases are solved using a diffuse interface model for two-phase flows with surface tension, phase change, and density and viscosity differences between the phases. This diffuse-interface model for flow is coupled with a phase-field equation for calculating the interface motion, and a species conservation equation for the gas transport. The model is validated for a single bubble growing inside a semi-infinite liquid, and convergence of the results with respect to the interface width is demonstrated. Large-scale numerical simulations for multiple bubbles inside a Hele-Shaw cell reveal the presence of complex interface dynamics and flows. The bubble dynamics, including coarsening and coalescence, are investigated as a function of the initial gas concentration, surface tension, and the density and viscosity contrasts between the phases.

  18. Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler.

    PubMed

    Meischen, Sandra J; Van Pelt, Vincent J; Zarate, Eugene A; Stephens, Edward A

    2004-01-01

    Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results. PMID:14871013

  19. Development of Numerical Simulation Method for Compressible Gas-Liquid Two-Phase Flows

    NASA Astrophysics Data System (ADS)

    Tamura, Y.

    2015-12-01

    A numerical simulation method of compressible gas-liquid two-phase flow is developed for analyses of a cavitation bubble. Thermodynamic state of both phases is described with stiffened gas equation of state. Interface of two phases is captured by Level-Set method. As internal energy jump between two phases is critical for the stability of computation, total energy equation is modified so that inviscid flux of energy is smoothly connected across the interface. Detail of governing equations as well as their discretization is described followed by the result of one-dimensional simple example computation.

  20. Photocatalytic/Magnetic Composite Particles

    NASA Technical Reports Server (NTRS)

    Wu, Chang-Yu; Goswami, Yogi; Garretson, Charles; Andino, Jean; Mazyck, David

    2007-01-01

    Photocatalytic/magnetic composite particles have been invented as improved means of exploiting established methods of photocatalysis for removal of chemical and biological pollutants from air and water. The photocatalytic components of the composite particles are formulated for high levels of photocatalytic activity, while the magnetic components make it possible to control the movements of the particles through the application of magnetic fields. The combination of photocatalytic and magnetic properties can be exploited in designing improved air- and water treatment reactors.

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

    PubMed Central

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

    2010-01-01

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

  2. DETERMINATION OF CHLOROETHENES IN ENVIRONMENTAL BIOLOGICAL SAMPLES USING GAS CHROMATOGRAPHY COUPLED WITH SOLID PHASE MICRO EXTRACTION

    EPA Science Inventory

    An analytical method has been developed to determine the chloroethene series, tetrachloroethene (PCE), trichloroethene (TCE),cisdichloroethene (cis-DCE) andtransdichloroethene (trans-DCE) in environmental biotreatment studies using gas chromatography coupled with a solid phase mi...

  3. Phase Separation and Pair Condensation in a Spin-Imbalanced 2D Fermi Gas.

    PubMed

    Mitra, Debayan; Brown, Peter T; Schauß, Peter; Kondov, Stanimir S; Bakr, Waseem S

    2016-08-26

    We study a two-component quasi-two-dimensional Fermi gas with imbalanced spin populations. We probe the gas at different interaction strengths and polarizations by measuring the density of each spin component in the trap and the pair momentum distribution after time of flight. For a wide range of experimental parameters, we observe in-trap phase separation characterized by the appearance of a spin-balanced core surrounded by a polarized gas. Our momentum space measurements indicate pair condensation in the imbalanced gas even for large polarizations where phase separation vanishes, pointing to the presence of a polarized pair condensate. Our observation of zero momentum pair condensates in 2D spin-imbalanced gases opens the way to explorations of more exotic superfluid phases that occupy a large part of the phase diagram in lower dimensions. PMID:27610853

  4. FACTORS INFLUENCING THE DEPOSITION OF A COMPOUND THAT PARTITIONS BETWEEN GAS AND PARTICULATE PHASES

    EPA Science Inventory

    How will atmospheric deposition behave for a compound when it reversibly sorbs between gas and atmospheric particulate phases? Two factors influence the answer. What physical mechanisms occur in the sorption process? What are the concentration and composition of atmospheric par...

  5. Gas Phase UTE MRI of Propane and Propene

    PubMed Central

    Kovtunov, Kirill V.; Romanov, Alexey S.; Salnikov, Oleg G.; Barskiy, Danila A.; Chekmenev, Eduard Y.; Koptyug, Igor V.

    2016-01-01

    1H MRI of gases can potentially enable functional lung imaging to probe gas ventilation and other functions. In this work, 1H MR images of hyperpolarized and thermally polarized propane gas were obtained using UTE (ultrashort echo time) pulse sequence. A 2D image of thermally polarized propane gas with ~0.9×0.9 mm2 spatial resolution was obtained in less than 2 seconds, demonstrating that even non-hyperpolarized hydrocarbon gases can be successfully utilized for conventional proton MRI. The experiments were also performed with hyperpolarized propane gas and demonstrated acquisition of high-resolution multi-slice FLASH 2D images in ca. 510 s and non slice-selective 2D UTE MRI images in ca. 2 s. The UTE approach adopted in this study can be potentially used for medical lung imaging. Furthermore, the possibility to combine UTE with selective suppression of 1H signals from one of the two gases in a mixture is demonstrated in this MRI study. The latter can be useful for visualizing industrially important processes where several gases may be present, e.g., gas-solid catalytic reactions. PMID:27478870

  6. Phase-field Modeling of Gas Bubbles and Thermal Conductivity Evolution in Nuclear Fuels

    SciTech Connect

    Hu, Shenyang Y.; Henager, Charles H.; Heinisch, Howard L.; Stan, Marius; Baskes, Michael I.; Valone, Steven

    2009-07-15

    The major factors that influence the thermal conductivity of the ceramics and metals are temperature, stoichiometry, microstructure, porosity, and point defects. Nuclear fuels and structure materials are subject to a severe radiation environment and their properties, including thermal conductivity change significantly with time and irradiation level. In particular, the accumulation of fission products and the formation of He bubbles can decrease the heat transfer, leading to overheating of the fuel element. In this work, we use the phase-field method to study the effect of microstructural changes on thermal conductivity. We developed a phase-field model to simulate the He bubble formation and growth in a single/polycrystalline material with defects. The model takes into account the generation of gas atoms and defects, gas atom diffusivity inhomogeneity, gas atom segregation, and gas bubble nucleation. With the model, we simulated the gas bubble and temperature evolution, and calculated the effect of gas bubble volume fraction on effective thermal conductivity.

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

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

  8. Sulfur hexafluoride: Optimal use as a gas-phase, infrared sensitizer

    SciTech Connect

    Stanley, A.E.; Ludwick, L.M.; White, D.; Andrews, D.E.; Godbey, S.E. )

    1992-12-01

    Investigations into the use of sulfur hexafluoride, SF[sub 6], as a gas-phase, infrared photochemical sensitizer have revealed several interesting phenomena. The expedient use of SF[sub 6] can produce an optimal quantity of nitrated product in the gas-phase, laser-induced nitration of cyclopentane. The optimal utilization of sulfur hexafluoride required critical optimization of both frequency and quantity. The results are described herein. 12 refs., 3 figs., 1 tab.

  9. Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

    SciTech Connect

    Hall G. E.; Goncharov, V.

    2012-05-29

    This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. Chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry are investigated by high resolution spectroscopic tools. Production, reaction, and energy transfer processes are investigated by transient, double resonance, polarization and saturation spectroscopies, with an emphasis on technique development and connection with theory, as well as specific molecular properties.

  10. Ultrafast electronic relaxation of excited state vitamin B 12 in the gas phase

    NASA Astrophysics Data System (ADS)

    Shafizadeh, Niloufar; Poisson, Lionel; Soep, Benoıˆt

    2008-06-01

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

  11. Conformational preferences of flavone and isoflavone in the gas phase, aqueous solution and organic solution

    NASA Astrophysics Data System (ADS)

    Ishiki, Hamilton Mitsugu; Alemán, Carlos; Galembeck, Sérgio Emanuel

    1998-05-01

    Flavone and isoflavone are an important class of secondary metabolites that are widely distributed in nature. In this Letter we have determined the conformational preferences of each compound in the gas phase, aqueous solution and organic solution. Gas-phase calculations were performed using AM1, MNDO, HF/3-21G, HF/6-31G(d) and B3-LYP/6-31G(d) calculations. Besides solution calculations were performed using the MST solvation model.

  12. Gas-Phase Molecular Dynamics: High Resolution Spectroscopy and Collision Dynamics of Transient Species

    SciTech Connect

    Hall, G.E.

    2011-05-31

    This research is carried out as part of the Gas-Phase Molecular Dynamics program in the Chemistry Department at Brookhaven National Laboratory. Chemical intermediates in the elementary gas-phase reactions involved in combustion chemistry are investigated by high resolution spectroscopic tools. Production, reaction, and energy transfer processes are investigated by transient, double resonance, polarization and saturation spectroscopies, with an emphasis on technique development and connection with theory, as well as specific molecular properties.

  13. Optical pyrometer based on the gas phase photoacoustic effect.

    PubMed

    Meng, Xiangling; Diebold, Gerald J

    2016-05-15

    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. PMID:27176967

  14. Formation of complex organic molecules in cold objects: the role of gas-phase reactions

    NASA Astrophysics Data System (ADS)

    Balucani, Nadia; Ceccarelli, Cecilia; Taquet, Vianney

    2015-04-01

    While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas-phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm ( ≳ 30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain-surface and gas-phase chemistry. We propose here a new model to form DME and MF with gas-phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthesized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairly well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas-phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

  15. APPLICATIONS ANALYSIS REPORT: ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS - THE REACTOR SYSTEM

    EPA Science Inventory

    This report details the Superfund Innovative Technology Evaluation of Eco Logic International's gas-phase chemical reduction process, with an emphasis on their Reactor System. he Eco Logic process employees a high temperature reactor filled with hydrogen gas as the means to destr...

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

    EPA Science Inventory

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

  17. A numerical study of two-phase flow in gas turbine combustors

    NASA Astrophysics Data System (ADS)

    Tolpadi, A. K.

    1992-07-01

    A method is presented for computing steady two-phase turbulent combusting flow in a gas turbine combustor. The gas phase equations are solved in an Eulerian frame of reference. The two-phase calculations are performed by using a liquid droplet spray combustion model and treating the motion of the evaporating fuel droplets in a Lagrangian frame of reference. The numerical algorithm employs nonorthogonal curvilinear coordinates, a multigrid iterative solution procedure, the standard k-epsilon turbulence model, and a combustion model made up of an assumed shape probability density function and the conserved scalar formulation. The trajectory computation of the fuel provides the source terms for all the gas phase equations. Results of the application of the two-phase model to a modern GE/SNECMA single annular CFM56 turbofan engine combustor are reported.

  18. Comparison of Gas and Adsorbed Phase X-ray Photoemission Spectra of Oxidized Organics on Ice

    NASA Astrophysics Data System (ADS)

    Newberg, J. T.; Bluhm, H.

    2011-12-01

    Most uptake studies of small chain organics on ice surfaces at near ambient conditions have been performed using flow tube and other methods which monitor the disappearance of the gas phase. We will present results using synchrotron based, ambient pressure X-ray photoemission spectroscopy which allows for the probing of the ice surface directly at near ambient conditions. C 1s XPS and C K-edge NEXAFS gas phase and adsorbed phase spectra will be compared for 2-propanol, acetone, and 1-propanal on ice at -45 C. Uptake experiments give rise to first order Langmuirian isotherms. Acetone and 2-propanol show little difference in the photoemission spectra between the gas phase and adsorbed phase, suggesting that adsorption occurs molecularly. However, adsorption of 1-propanal shows evidence of chemical transformation (oxidation) at the interface of ice. Further studies are underway to better understand this adsorption behavior.

  19. Phase transitions in a 3 dimensional lattice loop gas

    NASA Astrophysics Data System (ADS)

    MacKenzie, Richard; Nebia-Rahal, F.; Paranjape, M. B.

    2010-06-01

    We investigate, via Monte Carlo simulations, the phase structure of a system of closed, nonintersecting but otherwise noninteracting, loops in 3 Euclidean dimensions. The loops correspond to closed trajectories of massive particles and we find a phase transition as a function of their mass. We identify the order parameter as the average length of the loops at equilibrium. This order parameter exhibits a sharp increase as the mass is decreased through a critical value, the behavior seems to be a crossover transition. We believe that the model represents an effective description of the broken-symmetry sector of the 2+1 dimensional Abelian Higgs model, in the extreme strong coupling limit. The massive gauge bosons and the neutral scalars are decoupled, and the relevant low-lying excitations correspond to vortices and antivortices. The functional integral can be approximated by a sum over simple, closed vortex loop configurations. We present a novel fashion to generate nonintersecting closed loops, starting from a tetrahedral tessellation of three space. The two phases that we find admit the following interpretation: the usual Higgs phase and a novel phase which is heralded by the appearance of effectively infinitely long loops. We compute the expectation value of the Wilson loop operator and that of the Polyakov loop operator. The Wilson loop exhibits perimeter law behavior in both phases implying that the transition corresponds neither to the restoration of symmetry nor to confinement. The effective interaction between external charges is screened in both phases, however there is a dramatic increase in the polarization cloud in the novel phase as shown by the energy shift introduced by the Wilson loop.

  20. Industrial fuel gas plant project. Phase II. Memphis industrial fuel gas plant. Final report. [U-GAS process

    SciTech Connect

    Not Available

    1983-01-01

    The Industrial Fuel Gas Plant produces a nominal 50 billion Btu/day of product gas. The entire IFG production will be sold to MLGW. Under normal conditions, 20% of the output of the plant will be sold by MLGW to the local MAPCO refinery and exchanged for pipeline quality refinery gas. The MAPCO refinery gas will be inserted into the Memphis Natural Gas Distribution System. A portion (normally 10%) of the IFG output of the plant will be diverted to a Credit Generation Unit, owned by MLGW, where the IFG will be upgraded to pipeline quality (950 Btu/SCF). This gas will be inserted into MLGW's Natural Gas Distribution System. The remaining output of the IFG plant (gas with a gross heating value of 300 Btu/SCF) will be sold by MLGW as Industrial Fuel Gas. During periods when the IFG plant is partially or totally off-stream, natural gas from the Memphis Natural Gas Distribution System will be sent to an air mixing unit where the gas will be diluted to a medium Btu content and distributed to the IFG customers. Drawing 2200-1-50-00104 is the plant block flow diagram showing the process sequence and process related support facilities of this industrial plant. Each process unit as well as each process-related support facility is described briefly.

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

    SciTech Connect

    1994-09-01

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

  2. Gas phase dispersion in a small rotary kiln

    SciTech Connect

    Spencer, B.B.

    1981-07-01

    A study was made of nonideal flow of gas in a rotary kiln reactor. A rotating tube 0.165 m in diameter by 2.17 m long, with internal lifting flights, was operated at room temperature. Rotational speeds from 2.0 to 7.0 rpm, air flow rates from 0.351 to 4.178 m/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.

  3. AN ADVANCED FLUE GAS MONITOR FOR SO2 - PHASE I

    EPA Science Inventory

    The development of an instrument for continuously monitoring SO2 levels in flue gas is proposed. The SO2 will be detected by means of an electrochemical sensor cell, which operates in a three-electrode potentiostatic mode. The proposed innovation is develop-ment of an advan...

  4. NANOMATERIAL SOLUTIONS FOR HOT COAL GAS CLEANUP - PHASE I

    EPA Science Inventory

    Integrated gasification combined cycle (IGCC) is a new coal gasification technique that efficiently uses the hot (900-1500°C) generated syngas to power both steam and gas turbines. Due to regulations, this syngas must be free of sulfur and purification is normally carried ...

  5. Processes forming Gas, Tar, and Coke in Cellulose Gasification from Gas-Phase Reactions of Levoglucosan as Intermediate.

    PubMed

    Fukutome, Asuka; Kawamoto, Haruo; Saka, Shiro

    2015-07-01

    The gas-phase pyrolysis of levoglucosan (LG), the major intermediate species during cellulose gasification, was studied experimentally over the temperature range of 400-900 °C. Gaseous LG did not produce any dehydration products, which include coke, furans, and aromatic substances, although these are characteristic products of the pyrolysis of molten LG. Alternatively, at >500 °C, gaseous LG produced only fragmentation products, such as noncondensable gases and condensable C1 -C3 fragments, as intermediates during noncondensable gas formation. Therefore, it was determined that secondary reactions of gaseous LG can result in the clean (tar- and coke-free) gasification of cellulose. Cooling of the remaining LG in the gas phase caused coke formation by the transition of the LG to the molten state. The molecular mechanisms that govern the gas- and molten-phase reactions of LG are discussed in terms of the acid catalyst effect of intermolecular hydrogen bonding to promote the molten-phase dehydration reactions. PMID:26099988

  6. Selective transport of amino acids into the gas phase: driving forces for amino acid solubilization in gas-phase reverse micelles.

    PubMed

    Fang, Yigang; Bennett, Andrew; Liu, Jianbo

    2011-01-28

    We report a study on encapsulation of various amino acids into gas-phase sodium bis(2-ethylhexyl) sulfosuccinate (NaAOT) reverse micelles, using electrospray ionization guided-ion-beam tandem mass spectrometry. Collision-induced dissociation of mass-selected reverse micellar ions with Xe was performed to probe structures of gas-phase micellar assemblies, identify solute-surfactant interactions, and determine preferential incorporation sites of amino acids. Integration into gas-phase reverse micelles depends upon amino acid hydrophobicity and charge state. For examples, glycine and protonated amino acids (such as protonated tryptophan) are encapsulated within the micellar core via electrostatic interactions; while neutral tryptophan is adsorbed in the surfactant layer. As verified using model polar hydrophobic compounds, the hydrophobic effect and solute-interface hydrogen-bonding do not provide sufficient driving force needed for interfacial solubilization of neutral tryptophan. Neutral tryptophan, with a zwitterionic structure, is intercalated at the micellar interface between surfactant molecules through complementary effects of electrostatic interactions between tryptophan backbone and AOT polar heads, and hydrophobic interactions between tryptophan side chain and AOT alkyl tails. Protonation of tryptophan could significantly improve its incorporation capacity into gas-phase reverse micelles, and displace its incorporation site from the micellar interfacial zone to the core; protonation of glycine, on the other hand, has little effect on its encapsulation capacity. Another interesting observation is that amino acids of different isoelectric points could be selectively encapsulated into, and transported by, reverse micelles from solution to the gas phase, based upon their competition for protonation and subsequent encapsulation within the micellar core. PMID:21140022

  7. Gas phase condensation of superparamagnetic iron oxide-silica nanoparticles - control of the intraparticle phase distribution

    NASA Astrophysics Data System (ADS)

    Stötzel, C.; Kurland, H.-D.; Grabow, J.; Müller, F. A.

    2015-04-01

    Spherical, softly agglomerated and superparamagnetic nanoparticles (NPs) consisting of maghemite (γ-Fe2O3) and amorphous silica (SiO2) were prepared by CO2 laser co-vaporization (CoLAVA) of hematite powder (α-Fe2O3) and quartz sand (SiO2). The α-Fe2O3 portion of the homogeneous starting mixtures was gradually increased (15 mass%-95 mass%). It was found that (i) with increasing iron oxide content the NPs' morphology changes from a nanoscale SiO2 matrix with multiple γ-Fe2O3 inclusions to Janus NPs consisting of a γ-Fe2O3 and a SiO2 hemisphere to γ-Fe2O3 NPs each carrying one small SiO2 lens on its surface, (ii) the multiple γ-Fe2O3 inclusions accumulate at the NPs' inner surfaces, and (iii) all composite NPs are covered by a thin layer of amorphous SiO2. These morphological characteristics are attributed to (i) the phase segregation of iron oxide and silica within the condensed Fe2O3-SiO2 droplets, (ii) the temperature gradient within these droplets which arises during rapid cooling in the CoLAVA process, and (iii) the significantly lower surface energy of silica when compared to iron oxide. The proposed growth mechanism of these Fe2O3-SiO2 composite NPs during gas phase condensation can be transferred to other systems comprising a glass-network former and another component that is insoluble in the regarding glass. Thus, our model will facilitate the development of novel functional composite NPs for applications in biomedicine, optics, electronics, or catalysis.Spherical, softly agglomerated and superparamagnetic nanoparticles (NPs) consisting of maghemite (γ-Fe2O3) and amorphous silica (SiO2) were prepared by CO2 laser co-vaporization (CoLAVA) of hematite powder (α-Fe2O3) and quartz sand (SiO2). The α-Fe2O3 portion of the homogeneous starting mixtures was gradually increased (15 mass%-95 mass%). It was found that (i) with increasing iron oxide content the NPs' morphology changes from a nanoscale SiO2 matrix with multiple γ-Fe2O3 inclusions to Janus NPs

  8. Gas phase investigations of sulfonium salts by electrospray ft-icr/ms

    NASA Astrophysics Data System (ADS)

    Katritzky, Alan R.; Shipkova, Petia A.; Watson, Clifford H.; Eyler, John R.; Kevill, Dennis N.

    1997-11-01

    Twelve sulfonium salts were studied by electrospray Fourier transform ion cyclotron resonance mass spectrometry. Collisionally activated dissociation, CAD, reactions, using neutral argon as the collision gas, were performed to investigate dissociation pathways in the gas phase and to study the stabilizing/destabilizing effects of electron donating/withdrawing substituents on the sulfonium ions. Ion-molecule reactions were attempted to identify SN2 reaction mechanisms, but to date we have detected exclusively SN1-type reactions in the gas phase. Literature reports on the mass spectrometry of sulfonium cations are reviewed.

  9. Control of gas phase nanoparticle shape and its effect on MRI relaxivity

    NASA Astrophysics Data System (ADS)

    Aktaş, Sıtkı; Thornton, Stuart C.; Binns, Chris; Lari, Leonardo; Pratt, Andrew; Kröger, Roland; Horsfield, Mark A.

    2015-03-01

    We have used a sputtering gas aggregation source to produce Fe@FeO nanoparticles with different shapes, by annealing them at different temperatures in the gas phase. Without annealing, the most common shape found for the nanoparticles is cubic but annealing the nanoparticles at 1129 °C transforms the cubes into cuboctahedra. Measurements of the MRI relaxivity show that the cubic nanoparticles have a higher performance by a factor of two, which is attributed to a higher saturation magnetization for this shape. This indicates that the shape-control enabled by gas-phase synthesis is important for obtaining optimal performance in applications.

  10. A pressure cell for nonresonant inelastic x-ray scattering studies of gas phases

    SciTech Connect

    Minzer, M.; Bradley, J. A.; Musgrave, R.; Seidler, G. T.; Skilton, A.

    2008-08-15

    We report the design and performance of a gas-phase sample cell for measurements of momentum transfer (q) dependent nonresonant inelastic x-ray scattering (NRIXS). NRIXS measurements from He gas at 2 MPa (20 bars) readily demonstrate dipole-allowed and dipole-forbidden final states for two-electron excitations. Direct comparison of gas-phase NRIXS measurements with the corresponding nonresonant electron energy loss spectroscopy results (EELS) will be a valuable method for characterizing systematic errors in either technique for studies that require absolute normalization of the double differential cross section.

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

    PubMed

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

    2016-06-28

    Understanding of flow patterns and their transitions is significant to uncover the flow mechanics of two-phase flow. The local phase distribution and its fluctuations contain rich information regarding the flow structures. A wire-mesh sensor (WMS) was used to study the local phase fluctuations of horizontal gas-liquid two-phase flow, which was verified through comparing the reconstructed three-dimensional flow structure with photographs taken during the experiments. Each crossing point of the WMS is treated as a node, so the measurement on each node is the phase fraction in this local area. An undirected and unweighted flow pattern network was established based on connections that are formed by cross-correlating the time series of each node under different flow patterns. The structure of the flow pattern network reveals the relationship of the phase fluctuations at each node during flow pattern transition, which is then quantified by introducing the topological index of the complex network. The proposed analysis method using the WMS not only provides three-dimensional visualizations of the gas-liquid two-phase flow, but is also a thorough analysis for the structure of flow patterns and the characteristics of flow pattern transition. This article is part of the themed issue 'Supersensing through industrial process tomography'. PMID:27185959

  12. Double-side active TiO2-modified nanofiltration membranes in continuous flow photocatalytic reactors for effective water purification.

    PubMed

    Romanos, G Em; Athanasekou, C P; Katsaros, F K; Kanellopoulos, N K; Dionysiou, D D; Likodimos, V; Falaras, P

    2012-04-15

    A chemical vapour deposition (CVD) based innovative approach was applied with the purpose to develop composite TiO(2) photocatalytic nanofiltration (NF) membranes. The method involved pyrolytic decomposition of titanium tetraisopropoxide (TTIP) vapor and formation of TiO(2) nanoparticles through homogeneous gas phase reactions and aggregation of the produced intermediate species. The grown nanoparticles diffused and deposited on the surface of γ-alumina NF membrane tubes. The CVD reactor allowed for online monitoring of the carrier gas permeability during the treatment, providing a first insight on the pore efficiency and thickness of the formed photocatalytic layers. In addition, the thin TiO(2) deposits were developed on both membrane sides without sacrificing the high yield rates. Important innovation was also introduced in what concerns the photocatalytic performance evaluation. The membrane efficiency to photo degrade typical water pollutants, was evaluated in a continuous flow water purification device, applying UV irradiation on both membrane sides. The developed composite NF membranes were highly efficient in the decomposition of methyl orange exhibiting low adsorption-fouling tendency and high water permeability. PMID:21999989

  13. ANALYSIS OF A GAS-PHASE PARTITIONING TRACER TEST CONDUCTED THROUGH FRACTURED MEDIA

    EPA Science Inventory

    The gas-phase partitioning tracer method was used to estimate non-aqueous phase liquid (NAPL), water, and air saturations in the vadose zone at a chlorinated-solvent contaminated field site in Tucson, AZ. The tracer test was conducted in a fractured clay system that is the confin...

  14. Two parametric flow measurement in gas-liquid two-phase flow

    NASA Astrophysics Data System (ADS)

    Chen, Z.; Chen, C.; Xu, Y.; Zhao, Z.

    The importance and current development of two parametric measurement during two-phase flow are briefly reviewed in this paper. Gas-liquid two-phase two parametric metering experiments were conducted by using an oval gear meter and a sharp edged orifice mounted in series in a horizontal pipe. Compressed air and water were used as gas and liquid phases respectively. The correlations, which can be used to predict the total flow rate and volumetric quality of two-phase flow or volumetric flow rate of each phase, have also been proposed in this paper. Comparison of the calculated values of flow rate of each phase from the correlations with the test data showed that the root mean square fractional deviation for gas flow rate is 2.9 percent and for liquid flow rate 4.4 percent. The method proposed in this paper can be used to measure the gas and liquid flow rate in two-phase flow region without having to separate the phases.

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

    NASA Astrophysics Data System (ADS)

    Kis-Szabó, Krisztián; Szépfalusy, Péter; Szirmai, Gergely

    2007-05-01

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

  16. Separation of gas from liquid in a two-phase flow system

    NASA Technical Reports Server (NTRS)

    Hayes, L. G.; Elliott, D. G.

    1973-01-01

    Separation system causes jets which leave two-phase nozzles to impinge on each other, so that liquid from jets tends to coalesce in center of combined jet streams while gas phase is forced to outer periphery. Thus, because liquid coalescence is achieved without resort to separation with solid surfaces, cycle efficiency is improved.

  17. Gas distribution equipment in hydrogen service - Phase II

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

    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.

  18. Solution-phase synthesis and high photocatalytic activity of wurtzite ZnSe ultrathin nanobelts: a general route to 1D semiconductor nanostructured materials.

    PubMed

    Xiong, Shenglin; Xi, Baojuan; Wang, Chengming; Xi, Guangcheng; Liu, Xiaoyan; Qian, Yitai

    2007-01-01

    A general and facile synthetic route has been developed to prepare 1D semiconductor nanomaterials in a binary solution of distilled water and ethanol amine. The influence of the volume ratio of mixed solvents and reaction temperature on the yield and final morphology of products was investigated. Significantly, this is the first time that wurtzite ZnSe ultrathin nanobelts have been synthesized in solution. It has been confirmed that the photocatalytic activity of ZnSe nanobelts in the photodegradation of the fuchsine acid is higher than that of TiO(2) nanoparticles. The present work shows that the solvothermal route is facile, cheap, and versatile. Thus, it is very easy to realize scaled-up production, and brings new light on the synthesis and self-assembly of functional materials. PMID:17616961

  19. Spray characterization and gas phase interaction downstream of a simplified atomizer

    NASA Astrophysics Data System (ADS)

    Hebrard, P.; Trichet, P.; Millan, P.

    1992-07-01

    A detailed study of the flowfield produced by a simplified airblast atomizer was performed. This atomizer consists of an annular liquid sheet introduced into coflowing nonswirling and swirling air flow fields. Droplet size and velocity were measured in the resultant spray using a two components Phase/Doppler Particle Analyzer. A complete set of measurements was obtained at axial locations from 8 mm to 150 mm downstream from the nozzle. Laser velocimetry was also employed to measure the gas phase properties. The effect of swirl on droplet transport process is examined for this type of airblast atomizer and the results demonstrate the strong influence the spray has on the gas phase.

  20. Spectroscopic studies of kinetically trapped conformations in the gas phase: the case of triply protonated bradykinin.

    PubMed

    Voronina, Liudmila; Rizzo, Thomas R

    2015-10-21

    Understanding the relation between the gas-phase structure of biological molecules and their solution-phase structure is important when attempting to use gas-phase techniques to address biologically relevant questions. Directly after electrospray ionization, molecules can be kinetically trapped in a state that retains some "memory" of its conformation in solution and is separated from the lowest-energy gas-phase structure by barriers on the potential energy surface. In order to identify and characterize kinetically trapped structures, we have explored the conformational space of triply protonated bradykinin in the gas phase by combining field-asymmetric ion mobility spectrometry (FAIMS) with cold ion spectroscopy. We isolate three distinct conformational families and characterize them by recording their UV-photofragment spectra and vibrational spectra. Annealing of the initial conformational distribution produced by electrospray reveals that one of the conformational families is kinetically trapped, while two others are stable, gas-phase structures. We compare our results to previously published results obtained using drift-tube ion mobility spectrometry (IMS) and propose a correspondence between the conformational families separated by FAIMS and those by IMS. PMID:25940085

  1. Evolution of natural gas composition: Predictive multi-phase reaction-transport modeling

    SciTech Connect

    Ortoleva, P.J.; Chang, K.A.; Maxwell, J.M.

    1995-12-31

    A computational modeling approach is used to investigate reaction and transport processes affecting natural gas composition over geological time. Three basic stages are integrated -- gas generation from organic solids or liquids, interactions during source rock expulsion to the reservoir and reactions within the reservoir. Multi-phase dynamics is handled by solving the fully coupled problem of phase-to-phase transfer, intra-phase organic and inorganic reactions and redox and other reactions between fluid phase molecules and minerals. Effects of capillarity and relative permeability are accounted for. Correlations will be determined between gas composition, temperature history, the mineralogy of rocks with which the gas was in contact and the composition of source organic phases. Questions of H{sub 2}S scavenging by oxidizing minerals and the production or removal of CO{sub 2} are focused upon. Our three spatial dimensional, reaction-transport simulation approach has great promise for testing general concepts and as a practical tool for the exploration and production of natural gas.

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

    SciTech Connect

    Chen, C.; Thomas, D.M.

    1992-01-01

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

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

    SciTech Connect

    Chen, C.; Thomas, D.M.

    1992-12-31

    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.

  4. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    SciTech Connect

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-03-17

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase id dispersed.

  5. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    SciTech Connect

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-09-29

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase is dispersed.

  6. Two-phase turbine engines. [using gas-liquid mixture accelerated in nozzles

    NASA Technical Reports Server (NTRS)

    Elliott, D. G.; Hays, L. G.

    1976-01-01

    A description is given of a two-phase turbine which utilizes a uniform mixture of gas and liquid accelerated in nozzles of the types reported by Elliott and Weinberg (1968). The mixture acts directly on an axial flow or tangential impulse turbine or is separated into gas and liquid streams which operate separately on a gas turbine and a hydraulic turbine. The basic two-phase cycles are examined, taking into account working fluids, aspects of nozzle expansion, details of turbine cycle operation, and the effect of mixture ratio variation. Attention is also given to two-phase nozzle efficiency, two-phase turbine operating characteristics and efficiencies, separator turbines, and impulse turbine experiments.

  7. Dispersion and surface functionalization of oxide nanoparticles for transparent photocatalytic and UV-protecting coatings and sunscreens

    NASA Astrophysics Data System (ADS)

    Faure, Bertrand; Salazar-Alvarez, German; Ahniyaz, Anwar; Villaluenga, Irune; Berriozabal, Gemma; De Miguel, Yolanda R.; Bergström, Lennart

    2013-04-01

    This review describes recent efforts on the synthesis, dispersion and surface functionalization of the three dominating oxide nanoparticles used for photocatalytic, UV-blocking and sunscreen applications: titania, zinc oxide, and ceria. The gas phase and liquid phase synthesis is described briefly and examples are given of how weakly aggregated photocatalytic or UV-absorbing oxide nanoparticles with different composition, morphology and size can be generated. The principles of deagglomeration are reviewed and the specific challenges for nanoparticles highlighted. The stabilization of oxide nanoparticles in both aqueous and non-aqueous media requires a good understanding of the magnitude of the interparticle forces and the surface chemistry of the materials. Quantitative estimates of the Hamaker constants in various media and measurements of the isoelectric points for the different oxide nanoparticles are presented together with an overview of different additives used to prepare stable dispersions. The structural and chemical requirements and the various routes to produce transparent photocatalytic and nanoparticle-based UV-protecting coatings, and UV-blocking sunscreens are described and discussed.

  8. Gas-Phase Structures of Ketene and Acetic Acid from Acetic Anhydride Using Very-High-Temperature Gas Electron Diffraction.

    PubMed

    Atkinson, Sandra J; Noble-Eddy, Robert; Masters, Sarah L

    2016-03-31

    The gas-phase molecular structure of ketene has been determined using samples generated by the pyrolysis of acetic anhydride (giving acetic acid and ketene), using one permutation of the very-high-temperature (VHT) inlet nozzle system designed and constructed for the gas electron diffraction (GED) apparatus based at the University of Canterbury. The gas-phase structures of acetic anhydride, acetic acid, and ketene are presented and compared to previous electron diffraction and microwave spectroscopy data to show improvements in data extraction and manipulation with current methods. Acetic anhydride was modeled with two conformers, rather than a complex dynamic model as in the previous study, to allow for inclusion of multiple pyrolysis products. The redetermined gas-phase structure of acetic anhydride (obtained using the structure analysis restrained by ab initio calculations for electron diffraction method) was compared to that from the original study, providing an improvement on the description of the low vibrational torsions compared to the dynamic model. Parameters for ketene and acetic acid (both generated by the pyrolysis of acetic anhydride) were also refined with higher accuracy than previously reported in GED studies, with structural parameter comparisons being made to prior experimental and theoretical studies. PMID:26916368

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

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

    Electron-beam synthesis of liquid fuel from gaseous alkanes was upgraded for formation of conventional and alternative fuel from biomass or pyrolysis oil. Bio-feedstock conversion algorithm includes two consecutive stages: (1) initial macromolecules' transformation to low-molecular-weight intermediates; (2) transformation of these intermediates to stable fuel in gaseous alkanes' atmosphere. Radicals originated from alkanes participate in alkylation/hydrogenation of biomass intermediates. Chemical fixation of gaseous alkanes is amplified in the presence of biomass derivatives due to suppression of gas regeneration reactions, higher molar mass of reagents and lower volatility of radiolytic intermediates.

  10. Photolytic and photocatalytic degradation of 6-chloronicotinic acid.

    PubMed

    Zabar, Romina; Dolenc, Darko; Jerman, Tina; Franko, Mladen; Trebše, Polonca

    2011-10-01

    This work describes for the first time the photolytic and photocatalytic degradation of 6-chloronicotinic acid (6CNA) in double deionised water, which is a degradation product of neonicotinoid insecticides imidacloprid and acetamiprid, and it is known to appear in different environmental matrices. Photolytic experiments were performed with three UVA (ultraviolet A) polychromatic fluorescent lamps with broad maximum at 355 nm, while photocatalytic experiments were performed using immobilised titanium dioxide (TiO₂) on six glass slides in the spinning basket inside a photocatalytic quartz cell under similar irradiation conditions. Photolytic degradation revealed no change in concentration of 6CNA within 120 min of irradiation, while the photocatalytic degradation within 120 min, obeyed first-order kinetics. The observed disappearance rate constant was k=0.011 ± 0.001 min⁻¹ and t½ was 63.1 ± 5.5 min. Mineralisation rate was estimated through total organic carbon (TOC) and measurements revealed no carbon removal in case of photolysis after 120 min of exposure. However in photocatalytic experiments 46 ± 7% mineralisation was achieved within 120 min of irradiation. Nevertheless, the removal of total nitrogen (TN) was not observed across all experiments. Ion chromatographic analyses indicated transformation of chlorine atoms to chloride and increase of nitrate(V) ions only via photocatalytic experiments. Efficiency of selected advanced oxidation process (AOP) was investigated through toxicity assessment with Vibrio fischeri luminescent bacteria and revealed higher adverse effects of treated samples on bacteria following photocatalytic degradation in spite of the fact that higher mineralisation was achieved. New hydroxylated product generated in photocatalytic experiments with TiO₂, was confirmed with liquid chromatography-electro spray ionisation mass spectrometry (LC-ESI-MS/MS) analyses, gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic

  11. Analysis of Developing Gas/liquid Two-Phase Flows

    SciTech Connect

    Elena A. Tselishcheva; Michael Z. Podowski; Steven P. Antal; Donna Post Guillen; Matthias Beyer; Dirk Lucas

    2010-06-01

    The goal of this work is to develop a mechanistically based CFD model that can be used to simulate process equipment operating in the churn-turbulent regime. The simulations were performed using a state-of-the-art computational multiphase fluid dynamics code, NPHASE–CMFD [Antal et al,2000]. A complete four-field model, including the continuous liquid field and three dispersed gas fields representing bubbles of different sizes, was first carefully tested for numerical convergence and accuracy, and then used to reproduce the experimental results from the TOPFLOW test facility at Forschungszentrum Dresden-Rossendorf e.V. Institute of Safety Research [Prasser et al,2007]. Good progress has been made in simulating the churn-turbulent flows and comparison the NPHASE-CMFD simulations with TOPFLOW experimental data. The main objective of the paper is to demonstrate capability to predict the evolution of adiabatic churn-turbulent gas/liquid flows. The proposed modelling concept uses transport equations for the continuous liquid field and for dispersed bubble fields [Tselishcheva et al, 2009]. Along with closure laws based on interaction between bubbles and continuous liquid, the effect of height on air density has been included in the model. The figure below presents the developing flow results of the study, namely total void fraction at different axial locations along the TOPFLOW facility test section. The complete model description, as well as results of simulations and validation will be presented in the full paper.

  12. Development of a gas phase source for perfluoroalkyl acids to examine atmospheric sampling methods.

    PubMed

    MacInnis, John J; VandenBoer, Trevor C; Young, Cora J

    2016-06-21

    An inability to produce environmentally relevant gaseous mixing ratios of perfluoroalkyl acids (PFAAs), ubiquitous global contaminants, limits the analytical reliability of atmospheric chemists to make accurate gas and particulate measurements that are demonstrably free of interferences due to sampling artefacts. A gas phase source for PFAAs based on the acid displacement mechanism using perfluoropropionate (PFPrA), perfluorobutanoate (PFBA), perfluorohexanoate (PFHxA), and perfluorooctanoate (PFOA) has been constructed. The displacement efficiency of gas phase perfluorocarboxylic acids (PFCAs) is inversely related to chain length. Decreasing displacement efficiencies for PFPrA, PFBA, PFHxA, and PFOA were 90% ± 20%, 40% ± 10%, 40% ± 10%, 9% ± 4%, respectively. Generating detectable amounts of gas phase perfluorosulfonic acids (PFSAs) was not possible. It is likely that lower vapour pressure and much higher acidity play a role in this lack of emission. PFCA emission rates were not elevated by increasing relative humidity (25%-75%), nor flow rate of carrier gas from 33-111 sccm. Overall, reproducible gaseous production of PFCAs was within the error of the production of hydrochloric acid (HCl) as a displacing acid (±20%) and was accomplished using a dry nitrogen flow of 33 ± 2 sccm. A reproducible mass emission rate of 0.97 ± 0.10 ng min(-1) (n = 8) was observed for PFBA. This is equivalent to an atmospheric mixing ratio of 12 ppmv, which is easily diluted to environmentally relevant mixing ratios of PFBA. Conversely, generating gas phase perfluorononanoic acid (PFNA) by sublimating the solid acid under the same conditions produced a mass emission rate of 2800 ng min(-1), which is equivalent to a mixing ratio of 18 ppthv and over a million times higher than suspected atmospheric levels. Thus, for analytical certification of atmospheric sampling methods, generating gas phase standards for PFCAs is best accomplished using acid displacement under dry conditions

  13. Design of composite photocatalyst of TiO2 and Y-zeolite for degradation of 2-propanol in the gas phase under UV and visible light irradiation.

    PubMed

    Kamegawa, Takashi; Ishiguro, Yasushi; Kido, Ryota; Yamashita, Hiromi

    2014-01-01

    Hydrophobic Y-zeolite (SiO2/Al2O3 = 810) and TiO2 composite photocatalysts were designed by using two different types of TiO2 precursors, i.e., titanium ammonium oxalate and ammonium hexafluorotitanate. The porous structure, surface property and state of TiO2 were investigated by various characterization techniques. By using an ammonium hexafluorotitanate as a precursor, hydrophobic modification of the Y-zeolite surface and realizing visible light sensitivity was successfully achieved at the same time after calcination at 773 K in the air. The prepared sample still maintained the porous structure of Y-zeolite and a large surface area. Highly crystalline anatase TiO2 was also formed on the Y-zeolite surface by the role of fluorine in the precursor. The usages of ammonium hexafluorotitanate were effective for the improvement of the photocatalytic performance of the composite in the degradation of 2-propanol in the gas phase under UV and visible light (λ > 420 nm) irradiation. PMID:25314607

  14. Phase-field simulations of gas density within bubbles under irradiation

    SciTech Connect

    Paul C. Millett; Anter El-Azab; Michael Tonks

    2011-05-01

    Phase-field simulations are used to study the evolution of gas density within irradiation-induced bubbles. In our simulations, the dpa rate, gas production rate, and defect diffusivities are systematically varied to understand their effect on bubble nucleation rates, bubble densities, and the distribution of gas concentration within bubbles and in the solid regions. We find that gas densities within bubbles fluctuate drastically in the early nucleation stages, when growth rates are highest, but converge to steady-state values during the later coarsening stages. The steady-state gas densities within bubbles correspond with the ratio of total accumulated vacancy content divided by the total accumulated gas content, in agreement with a thermodynamic analysis concerning free-energy minimization.

  15. Photocatalytic reduction of CO2 over Ag/TiO2 nanocomposites prepared with a simple and rapid silver mirror method.

    PubMed

    Yu, Bingcheng; Zhou, Yong; Li, Peng; Tu, Wenguang; Li, Ping; Tang, Lanqin; Ye, Jinhua; Zou, Zhigang

    2016-06-01

    The photocatalytic reduction of CO2 over Ag/TiO2 composites prepared with a simple silver mirror reaction method was investigated under UV-visible irradiation in both gas-phase (CO2 + water vapor) and aqueous solution (CO2-saturated NaHCO3 solution) systems. The as-prepared Ag/TiO2 nanocomposite exhibits efficient photocatalytic activity due to the surface plasmonic resonance and electron sink effect of the Ag component, which was found to be closely related to the size and loading amount of Ag. The rapid silver method is effective at curbing the size of Ag, so photocatalytic activity can be improved. Diverse organic chemical products were detected, including mainly methane and methanol as well as a small amount of C2 and C3 species such as acetaldehyde and acetone. Possible photocatalytic mechanisms were proposed. This artificial photosynthesis process may give a prosperous route to the removal of CO2 while simultaneously converting CO2 to valuable fuels based on highly efficient photocatalysts. PMID:27231820

  16. Novel characterization of the aerosol and gas-phase composition of aerosolized jet fuel.

    PubMed

    Tremblay, Raphael T; Martin, Sheppard A; Fisher, Jeffrey W

    2010-04-01

    Few robust methods are available to characterize the composition of aerosolized complex hydrocarbon mixtures. The difficulty in separating the droplets from their surrounding vapors and preserving their content is challenging, more so with fuels, which contain hydrocarbons ranging from very low to very high volatility. Presented here is a novel method that uses commercially available absorbent tubes to measure a series of hydrocarbons in the vapor and droplets from aerosolized jet fuels. Aerosol composition and concentrations were calculated from the differential between measured total (aerosol and gas-phase) and measured gas-phase concentrations. Total samples were collected directly, whereas gas-phase only samples were collected behind a glass fiber filter to remove droplets. All samples were collected for 1 min at 400 ml min(-1) and quantified using thermal desorption-gas chromatography-mass spectrometry. This method was validated for the quantification of the vapor and droplet content from 4-h aerosolized jet fuel exposure to JP-8 and S-8 at total concentrations ranging from 200 to 1000 mg/m(3). Paired samples (gas-phase only and total) were collected every approximately 40 min. Calibrations were performed with neat fuel to calculate total concentration and also with a series of authentic standards to calculate specific compound concentrations. Accuracy was good when compared to an online GC-FID (gas chromatography-flame ionization detection) technique. Variability was 15% or less for total concentrations, the sum of all gas-phase compounds, and for most specific compound concentrations in both phases. Although validated for jet fuels, this method can be adapted to other hydrocarbon-based mixtures. PMID:20218763

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

    NASA Astrophysics Data System (ADS)

    Kong, Michael

    2014-10-01

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

  18. Functional and metabolic properties of alveolar macrophages in response to the gas phase of tobacco smoke.

    PubMed Central

    Drath, D B; Shorey, J M; Huber, G L

    1981-01-01

    The effect of whole tobacco smoke and the gas phase of tobacco smoke on the metabolism and phagocytic ability of alveolar macrophages was monitored over a 30-day exposure period. It was demonstrated that both the gas phase and whole tobacco smoke induced a weight loss in exposed rats. Alveolar macrophage oxygen consumption was markedly increased by both exposure regimens. Superoxide generation was not affected by whole tobacco smoke exposure but was increased in response to the filtered gas phase. Hexose monophosphate shunt activity was not altered by either treatment. When metabolic alterations were seen in response to the separate exposures, they were seen only after a phagocytic challenge to the macrophage and not when the cell was unchallenged. Neither whole tobacco smoke nor the gas phase had any significant effect on the ability of alveolar macrophages to phagocytize a viable challenge of Staphylococcus aureus. Our results suggest that many of the metabolic and functional effects of tobacco smoke on alveolar macrophages can be attributed to the gas-phase component of whole tobacco smoke. PMID:6271676

  19. Functional and metabolic properties of alveolar macrophages in response to the gas phase of tobacco smoke.

    PubMed

    Drath, D B; Shorey, J M; Huber, G L

    1981-10-01

    The effect of whole tobacco smoke and the gas phase of tobacco smoke on the metabolism and phagocytic ability of alveolar macrophages was monitored over a 30-day exposure period. It was demonstrated that both the gas phase and whole tobacco smoke induced a weight loss in exposed rats. Alveolar macrophage oxygen consumption was markedly increased by both exposure regimens. Superoxide generation was not affected by whole tobacco smoke exposure but was increased in response to the filtered gas phase. Hexose monophosphate shunt activity was not altered by either treatment. When metabolic alterations were seen in response to the separate exposures, they were seen only after a phagocytic challenge to the macrophage and not when the cell was unchallenged. Neither whole tobacco smoke nor the gas phase had any significant effect on the ability of alveolar macrophages to phagocytize a viable challenge of Staphylococcus aureus. Our results suggest that many of the metabolic and functional effects of tobacco smoke on alveolar macrophages can be attributed to the gas-phase component of whole tobacco smoke. PMID:6271676

  20. Air-sea transfer of gas phase controlled compounds

    NASA Astrophysics Data System (ADS)

    Yang, M.; Bell, T. G.; Blomquist, B. W.; Fairall, C. W.; Brooks, I. M.; Nightingale, P. D.

    2016-05-01

    Gases in the atmosphere/ocean have solubility that spans several orders of magnitude. Resistance in the molecular sublayer on the waterside limits the air-sea exchange of sparingly soluble gases such as SF6 and CO2. In contrast, both aerodynamic and molecular diffusive resistances on the airside limit the exchange of highly soluble gases (as well as heat). Here we present direct measurements of air-sea methanol and acetone transfer from two open cruises: the Atlantic Meridional Transect in 2012 and the High Wind Gas Exchange Study in 2013. The transfer of the highly soluble methanol is essentially completely airside controlled, while the less soluble acetone is subject to both airside and waterside resistances. Both compounds were measured concurrently using a proton-transfer-reaction mass spectrometer, with their fluxes quantified by the eddy covariance method. Up to a wind speed of 15 m s-1, observed air-sea transfer velocities of these two gases are largely consistent with the expected near linear wind speed dependence. Measured acetone transfer velocity is ∼30% lower than that of methanol, which is primarily due to the lower solubility of acetone. From this difference we estimate the “zero bubble” waterside transfer velocity, which agrees fairly well with interfacial gas transfer velocities predicted by the COARE model. At wind speeds above 15 m s-1, the transfer velocities of both compounds are lower than expected in the mean. Air-sea transfer of sensible heat (also airside controlled) also appears to be reduced at wind speeds over 20 m s-1. During these conditions, large waves and abundant whitecaps generate large amounts of sea spray, which is predicted to alter heat transfer and could also affect the air-sea exchange of soluble trace gases. We make an order of magnitude estimate for the impacts of sea spray on air-sea methanol transfer.

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

    NASA Astrophysics Data System (ADS)

    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

  2. Determining the properties of gas-phase clusters

    NASA Astrophysics Data System (ADS)

    Hopkins, W. Scott

    2015-11-01

    As our understanding of clusters has improved, we have found that rather than being models for surface and condensed phase phenomena, clusters often display chemical and physical properties that are quite distinct from those of their atomic constituents or associated bulk materials. Indeed, identifying and utilising the unique properties of dimensionally confined species is a major theme in nanotechnology. Consequently, numerous experimental and computational methods have been employed to investigate the structures and properties of cluster systems. In this article, the techniques of infrared multiple photon dissociation and differential mobility spectrometry are discussed using the examples of [Ag.B12F12]- and tetraalkylammonium/solvent ionic clusters, respectively.

  3. Gas phase contributions to topochemical hydride reduction reactions

    NASA Astrophysics Data System (ADS)

    Kobayashi, Yoji; Li, Zhaofei; Hirai, Kei; Tassel, Cédric; Loyer, François; Ichikawa, Noriya; Abe, Naoyuki; Yamamoto, Takafumi; Shimakawa, Yuichi; Yoshimura, Kazuyoshi; Takano, Mikio; Hernandez, Olivier J.; Kageyama, Hiroshi

    2013-11-01

    Alkali and alkali earth hydrides have been used as solid state reductants recently to yield many interesting new oxygen-deficient transition metal oxides. These reactions have tacitly been assumed to be a solid phase reaction between the reductant and parent oxide. We have conducted a number of experiments with physical separation between the reductant and oxides, and find that in some cases reduction proceeds even when the reagents are physically separated, implying reactions with in-situ generated H2 and, to a lesser extent, getter mechanisms. Our findings change our understanding of these topochemical reactions, and should enhance the synthesis of additional new oxides and nanostructures.

  4. Measurements of liquid-phase turbulence in gas-liquid two-phase flows using particle image velocimetry

    NASA Astrophysics Data System (ADS)

    Zhou, Xinquan; Doup, Benjamin; Sun, Xiaodong

    2013-12-01

    Liquid-phase turbulence measurements were performed in an air-water two-phase flow loop with a circular test section of 50 mm inner diameter using a particle image velocimetry (PIV) system. An optical phase separation method--planar laser-induced fluorescence (PLIF) technique—which uses fluorescent particles and an optical filtration technique, was employed to separate the signals of the fluorescent seeding particles from those due to bubbles and other noises. An image pre-processing scheme was applied to the raw PIV images to remove the noise residuals that are not removed by the PLIF technique. In addition, four-sensor conductivity probes were adopted to measure the radial distribution of the void fraction. Two benchmark tests were performed: the first was a comparison of the PIV measurement results with those of similar flow conditions using thermal anemometry from previous studies; the second quantitatively compared the superficial liquid velocities calculated from the local liquid velocity and void fraction measurements with the global liquid flow rate measurements. The differences of the superficial liquid velocity obtained from the two measurements were bounded within ±7% for single-phase flows and two-phase bubbly flows with the area-average void fraction up to 18%. Furthermore, a preliminary uncertainty analysis was conducted to investigate the accuracy of the two-phase PIV measurements. The systematic uncertainties due to the circular pipe curvature effects, bubble surface reflection effects and other potential uncertainty sources of the PIV measurements were discussed. The purpose of this work is to facilitate the development of a measurement technique (PIV-PLIF) combined with image pre-processing for the liquid-phase turbulence in gas-liquid two-phase flows of relatively high void fractions. The high-resolution data set can be used to more thoroughly understand two-phase flow behavior, develop liquid-phase turbulence models, and assess high

  5. Modification of C/TiO2@MCM-41 with nickel nanoparticles for photocatalytic desulfurization enhancement of a diesel fuel model under visible light.

    PubMed

    Zarrabi, M; Entezari, M H

    2015-11-01

    Ni metal nanoparticles were attached on the C/TiO2@MCM-41 (CTM-41) via facile and fast method based on dispersing of C/TiO2@MCM-41 in aqueous solution containing nickel ions by ultrasonic bath. Then, for the first time, the Ni ions were converted to Ni nanoparticles under UV light (photo-assisted deposition, PAD method), without using reducing agents and hydrogen gas. This process was carried out under the relatively mild conditions. The results showed that Ni (II) was reduced to Ni metallic nanoparticle in the size of about 2.7 nm on the surface of CTM-41 (Ni/CTM-41) with specific surface area of 754.37 m(2) g(-1). The photocatalytic ultra-deep desulfurization of a fuel-like n-octane containing dibenzothiophene (DBT) was conducted over the Ni/CTM-41 nanophotocatalyst. Using this method, the total sulfur content efficiently decreased under mild conditions in one phase and without using an oxidant. The synthesized Ni/CTM-41 (3% Ni) exhibited the maximum photocatalytic desulfurization of DBT for all different ratios of Si/Ti. In contrast, the synthesized CTM-41 (without Ni) exhibited the maximum photocatalytic desulfurization of DBT only for minimum ratio of Si/Ti. The Ni/CTM-41 was characterized by several techniques including N2 adsorption-desorption isotherms, XRD, TEM, and atomic absorption spectroscopy techniques. The results confirmed that Ni was highly dispersed on the support phase. The GC-MS analysis confirmed the photocatalytic removal of DBT. Based on the experimental results, it is proposed that the hydroxyl radical and hole have key role in the photocatalytic desulfurization process. PMID:26196719

  6. Method of photocatalytic nanotagging

    DOEpatents

    Shelnutt, John A.; Medforth, Craig J.; Song, Yujiang

    2010-04-27

    A nanotagged chemical structure comprising a chemical structure with an associated photocatalyst and a tagging nanoparticle (a nanotag) grown in proximity to the photocatalyst, and a method for making the nanotagged chemical structure. The nanoparticle is grown in proximity to the photocatalyst by using a photocatalytic reduction reaction.

  7. Test plan for phase II of the Retained Gas Sampler system

    SciTech Connect

    Hey, B.E.

    1995-06-19

    The Retained Gas Sampler (RGS) system is being developed to permit characterization of the gas phase component of waste tank core samples. Several laboratory experiments have been conducted which have affirmed the proof-of-principle for separating the gas phase materials from waste tank material in a quantitative manner. However, experiments conducted thus far have dealt only with representative materials and simulated hardware mock-ups. This test plan deals with the operation and testing of actual devices in the hot cell environment. This test plan coves all aspects of the RGS system including: sampler load-in, extrusion, gas extraction, quantitative separation, sample collection, and quantitative analysis. Sample material used in this test plan will be waste tank simulants and will not be radioactive. The work environment, however, will be an operating hot cell facility and will have radioactive contaminated surfaces. Operation of the system will therefore require an official radiation work permit (RWP).

  8. Device for two-dimensional gas-phase separation and characterization of ion mixtures

    DOEpatents

    Tang, Keqi; Shvartsburg, Alexandre A.; Smith, Richard D.

    2006-12-12

    The present invention relates to a device for separation and characterization of gas-phase ions. The device incorporates an ion source, a field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer, an ion mobility spectrometry (IMS) drift tube, and an ion detector. In one aspect of the invention, FAIMS operating voltages are electrically floated on top of the IMS drift voltage. In the other aspect, the FAIMS/IMS interface is implemented employing an electrodynamic ion funnel, including in particular an hourglass ion funnel. The present invention improves the efficiency (peak capacity) and sensitivity of gas-phase separations; the online FAIMS/IMS coupling creates a fundamentally novel two-dimensional gas-phase separation technology with high peak capacity, specificity, and exceptional throughput.

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

    SciTech Connect

    Read, Douglas; Sillerud, Colin Halliday

    2016-01-01

    The overarching goal of this project is to integrate Sandia's microfabricated gas-chromatography ( GC) columns with a stationary phase material that is capable of retaining high-volatility chemicals and permanent gases. The successful integration of such a material with GCs would dramatically expand the repertoire of detectable compounds for Sandia's various microanalysis systems. One such promising class of candidate materials is metal-organic frameworks (MOFs). In this report we detail our methods for controlled deposition of HKUST-1 MOF stationary phases within GC columns. We demonstrate: the chromatographic separation of natural gas; a method for determining MOF film thickness from chromatography alone; and the first-reported GC x GC separation of natural gas -- in general -- let alone for two disparate MOF stationary phases. In addition we determine the fundamental thermodynamic constant for mass sorption, the partition coefficient, for HKUST-1 and several light hydrocarbons and select toxic industrial chemicals.

  10. Measurement of gas-phase ionic mercury(II) species in ambient air

    SciTech Connect

    Stratton, W.J.; Lindberg, S.E.

    1995-12-31

    One of the important questions in the biogeochemical cycling of mercury is the speciation of mercury in the atmosphere. Although a large fraction of Hg in ambient air is Hg(O), a small fraction is believed to be gas-phase Hg(II). This fraction is highly water-soluble and thus is important to explaining the high concentration of Hg in precipitation. We have developed a novel technique for measuring gas-phase Hg(II), using a high-flow refluxing mist chamber to trap the water-soluble Hg(II) in an aerosol mist. Measured concentrations of gas-phase Hg(II) in ambient air are generally in the range 0.05-0.1 ng/m{sup 3}, or 2-4% of the total gaseous Hg. In this talk, representative data under different atmospheric and geographic conditions will be presented, along with a summary of some of the experimental difficulties and unanswered questions.

  11. Discontinuous phase transition in a dimer lattice gas

    NASA Astrophysics Data System (ADS)

    Dickman, Ronald

    2012-05-01

    I study a dimer model on the square lattice with nearest neighbor exclusion as the only interaction. Detailed simulations using tomographic entropic sampling show that as the chemical potential is varied, there is a strongly discontinuous phase transition, at which the particle density jumps by about 18% of its maximum value, 1/4. The transition is accompanied by the onset of orientational order, to an arrangement corresponding to the {1/2, 0, 1/2} structure identified by Phares et al. [Physica B 409, 1096 (2011)] in a dimer model with finite repulsion at fixed density. Using finite-size scaling and Binder's cumulant, the expected scaling behavior at a discontinuous transition is verified in detail. The discontinuous transition can be understood qualitatively given that the model possesses eight equivalent maximum-density configurations, so that its coarse-grained description corresponds to that of the q = 8 Potts model.

  12. Gas-phase chemiluminescence and chemi-ionization

    SciTech Connect

    Fontijn, A.

    1985-01-01

    The phenomena of chemiluminescence (or more broadly chemi-excitation) and chemi-ionization have major similarities from a fundamental kinetic and dynamic point of view. However, since the former has primarily been investigated using optical spectroscopic techniques and the latter largely by mass spectroscopic (and other gaseous electronic) methods, the two phenomena have apparently never, explicitly been discussed together in one volume. In addition to a number of review articles on each individual subject, several meetings and books have had chemiluminescence and bioluminescence as their theme and those have been dominated by condensed phase work. On the other hand, chemi-ionization is often discussed in the contest of gaseous electronics, plasma chemistry and combustion. It is the goal of this book to present a more unified understanding of the two phenomena.

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

    SciTech Connect

    D. W. Simmons

    1994-09-01

    The gas phase decontamination project is investigating the use of chlorine trifluoride (ClF{sub 3}) to fluorinate nonvolatile uranium deposits to produce uranium hexafluoride (UF{sub 6}) gas. The potential existence of chlorine dioxide (ClO{sub 2}) during gas phase decontamination with ClF{sub 3} has been the subject of recent safety discussions. Some of the laboratory data collected during feasibility studies of the gas phase process has been evaluated for the presence of ClO{sub 2} in the product gas stream. The preliminary evidence to date can be summarized as follows: (1) ClO{sub 2} was not detected in the flow loop in the absence of ClF{sub 3}; (2) ClO{sub 2} was not detected in the static reactors in the absence of both ClF{sub 3} and ClF; and (3) ClO{sub 2} was detected in a static reactor in the absence of all fluorinating gases. The experimental evidence suggests that ClO{sub 2} will not exist in the presence of ClF{sub 3}, ClF, or UF{sub 6}. The data analyzed to date is insufficient to determine the stability of ClO{sub 2} in the presence of ClO{sub 2}F. Thermodynamic calculations of the ClF{sub 3} + H{sub 2}O system support the experimental evidence, and suggest that ClO{sub 2} will not exist in the presence of ClO{sub 2}F. Additional experimental efforts are needed to provide a better understanding of the gas phase ClF{sub 3} treatments and the product gases. However, preliminary evidence to date suggests that ClO{sub 2} should not be present as a product during the normal operations of the gas phase decontamination project.

  14. Polymerization in the gas phase, in clusters, and on nanoparticle surfaces.

    PubMed

    El-Shall, M Samy

    2008-07-01

    Gas phase and cluster experiments provide unique opportunities to quantitatively study the effects of initiators, solvents, chain transfer agents, and inhibitors on the mechanisms of polymerization. Furthermore, a number of important phenomena, unique structures, and novel properties may exist during gas-phase and cluster polymerization. In this regime, the structure of the growing polymer may change dramatically and the rate coefficient may vary significantly upon the addition of a single molecule of the monomer. These changes would be reflected in the properties of the oligomers deposited from the gas phase. At low pressures, cationic and radical cationic polymerizations may proceed in the gas phase through elimination reactions. In the same systems at high pressure, however, the ionic intermediates may be stabilized, and addition without elimination may occur. In isolated van der Waals clusters of monomer molecules, sequential polymerization with several condensation steps can occur on a time scale of a few microseconds following the ionization of the gas-phase cluster. The cluster reactions, which bridge gas-phase and condensed-phase chemistry, allow examination of the effects of controlled states of aggregation. This Account describes several examples of gas-phase and cluster polymerization studies where the most significant results can be summarized as follows: (1) The carbocation polymerization of isobutene shows slower rates with increasing polymerization steps resulting from entropy barriers, which could explain the need for low temperatures for the efficient propagation of high molecular weight polymers. (2) Radical cation polymerization of propene can be initiated by partial charge transfer from an ionized aromatic molecule such as benzene coupled with covalent condensation of the associated propene molecules. This novel mechanism leads exclusively to the formation of propene oligomer ions and avoids other competitive products. (3) Structural information

  15. Gas adsorption/absorption heat switch, phase 1

    NASA Technical Reports Server (NTRS)

    Chan, C. K.

    1987-01-01

    The service life and/or reliability of far-infrared sensors on surveillance satellites is presently limited by the cryocooler. The life and/or reliability, however, can be extended by using redundant cryocoolers. To reduce parasitic heat leak, each stage of the inactive redundant cryocooler must be thermally isolated from the optical system, while each stage of the active cryocooler must be thermally connected to the system. The thermal break or the thermal contact can be controlled by heat switches. Among different physical mechanisms for heat switching, mechanically activated heat switches tend to have low reliability and, furthermore, require a large contact force. Magnetoresistive heat switches are, except at very low temperatures, of very low efficiency. Heat switches operated by the heat pipe principle usually require a long response time. A sealed gas gap heat switch operated by an adsorption pump has no mechanical motion and should provide the reliability and long lifetime required in long-term space missions. Another potential application of a heat switch is the thermal isolation of the optical plane during decontamination.

  16. CFD simulation of single-phase and two-phase flow in gas-liquid cylindrical cyclone separators

    SciTech Connect

    Erdal, F.M.; Shirazi, S.A.; Shoham, O.; Kouba, G.E.

    1996-12-31

    The petroleum industry has shown interest in utilizing the Gas Liquid Cylindrical Cyclone (GLCC) separator as an alternative to the vessel-type separator. Thus, it is important to develop predictive tools for design and to be able to improve the technology of the GLCC. Previous studies have resulted in mechanistic models capable of predicting the operational envelope for liquid carry-over. However, these models do not address details of the complex flow field in the GLCC and related phenomena such as gas carry-under. This paper presents computational fluid dynamics (CFD) simulations of single-phase and- two-phase flow in several GLCC configurations. The CFD simulations are compared with experimental data including tangential velocity profiles and tangential velocity decay. Good agreement is observed between the data and the simulations. An axisymmetric flow model for the GLCC is also developed. The axisymmetric model, which is computationally efficient, gives good results as compared to the three-dimensional simulations. Preliminary two-phase flow simulations are also performed to predict the gas void fraction distribution in the GLCC.

  17. Amphipols Outperform Dodecylmaltoside Micelles in Stabilizing Membrane Protein Structure in the Gas Phase

    PubMed Central

    2014-01-01

    Noncovalent mass spectrometry (MS) is emerging as an invaluable technique to probe the structure, interactions, and dynamics of membrane proteins (MPs). However, maintaining native-like MP conformations in the gas phase using detergent solubilized proteins is often challenging and may limit structural analysis. Amphipols, such as the well characterized A8-35, are alternative reagents able to maintain the solubility of MPs in detergent-free solution. In this work, the ability of A8-35 to retain the structural integrity of MPs for interrogation by electrospray ionization-ion mobility spectrometry-mass spectrometry (ESI-IMS-MS) is compared systematically with the commonly used detergent dodecylmaltoside. MPs from the two major structural classes were selected for analysis, including two β-barrel outer MPs, PagP and OmpT (20.2 and 33.5 kDa, respectively), and two α-helical proteins, Mhp1 and GalP (54.6 and 51.7 kDa, respectively). Evaluation of the rotationally averaged collision cross sections of the observed ions revealed that the native structures of detergent solubilized MPs were not always retained in the gas phase, with both collapsed and unfolded species being detected. In contrast, ESI-IMS-MS analysis of the amphipol solubilized MPs studied resulted in charge state distributions consistent with less gas phase induced unfolding, and the presence of lowly charged ions which exhibit collision cross sections comparable with those calculated from high resolution structural data. The data demonstrate that A8-35 can be more effective than dodecylmaltoside at maintaining native MP structure and interactions in the gas phase, permitting noncovalent ESI-IMS-MS analysis of MPs from the two major structural classes, while gas phase dissociation from dodecylmaltoside micelles leads to significant gas phase unfolding, especially for the α-helical MPs studied. PMID:25495802

  18. Contributions of gas-phase plasma chemistry to surface modifications and gas-surface interactions: investigations of fluorocarbon rf plasmas

    NASA Astrophysics Data System (ADS)

    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

  19. Distribution of Organophosphate Esters between the Gas and Particle Phase-Model Predictions vs Measured Data.

    PubMed

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

    2016-07-01

    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) < 10 and a subcooled liquid vapor pressure (log PL) > -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. PMID:27144674

  20. Gas-phase formation of silicon carbides, oxides, and sulphides from atomic silicon ions

    NASA Technical Reports Server (NTRS)

    Bohme, Diethard K.; Wlodek, Stanislaw; Fox, Arnold

    1989-01-01

    A systematic experimental study of the kinetics and mechanisms of the chemical reactions in the gas phase between ground-state Si(+)2p and a variety of astrophysical molecules. The aim of this study is to identify the reactions which trigger the formation of chemical bonds between silicon and carbon, oxygen and sulphur, and the chemical pathways which lead to further molecular growth. Such knowledge is valuable in the identification of new extraterrestrial silicon-bearing molecules and for an assessment of the gas-phase transition from atomic silicon to silicon carbide and silicate grain particles in carbon-rich and oxygen-rich astrophysical environments.

  1. Gas Phase Spectra and Structural Determination of Glucose 6 Phosphate Using Cryogenic Ion Vibrational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Kregel, Steven J.; Voss, Jonathan; Marsh, Brett; Garand, Etienne

    2014-06-01

    Glucose-6-Phosphate (G6P) is one member of a class of simple phosphorylated sugars that are relevant in biological processes. We have acquired a gas phase infrared spectrum of G6P- using cryogenic ion vibrational spectroscopy (CIVS) in a home-built spectrometer. The experimental spectrum was compared with calculated vibrational spectra from a systematic conformer search. For both of the α and β anomers, results show that only the lowest energy conformers are present in the gas phase. If spectral signatures for similar sugars could be cataloged, it would allow for conformer-specific determination of mixture composition, for example, for glycolyzation processes.

  2. Characterization of annular two-phase gas-liquid flows in microgravity

    NASA Technical Reports Server (NTRS)

    Bousman, W. Scott; Mcquillen, John B.

    1994-01-01

    A series of two-phase gas-liquid flow experiments were developed to study annular flows in microgravity using the NASA Lewis Learjet. A test section was built to measure the liquid film thickness around the perimeter of the tube permitting the three dimensional nature of the gas-liquid interface to be observed. A second test section was used to measure the film thickness, pressure drop and wall shear stress in annular microgravity two-phase flows. Three liquids were studied to determine the effects of liquid viscosity and surface tension. The result of this study provide insight into the wave characteristics, pressure drop and droplet entrainment in microgravity annular flows.

  3. Time-dependent gas phase kinetics in a hydrogen diluted silane plasma

    SciTech Connect

    Nunomura, S.; Kondo, M.; Yoshida, I.

    2009-02-16

    The gas phase kinetics in a high-pressure hydrogen diluted silane plasma has been studied at time scales of 10{sup -2}-6x10{sup 2} s. The time-resolved gas phase composition shows the following kinetics at different time scales: silane decomposition and polysilane generation in < or approx. 2x10{sup -1} s, nanoparticle formation and plasma density reduction in 10{sup -1}-10{sup 0} s, polysilane accumulation in 10{sup 0}-10{sup 2} s, and silane depletion and electrode heating in > or approx. 10{sup 1} s. Disilane radicals are implied to be the dominant film precursors in addition to silyl radicals.

  4. Study of Hind Limb Tissue Gas Phase Formation in Response to Suspended Adynamia and Hypokinesia

    NASA Technical Reports Server (NTRS)

    Butler, Bruce D.

    1996-01-01

    The purpose of this study was to investigate the hypothesis that reduced joint/muscle activity (hypo kinesia) as well as reduced or null loading of limbs (adynamia) in gravity would result in reduced decompression-induced gas phase and symptoms of decompression sickness (DCS). Finding a correlation between the two phenomena would correspond to the proposed reduction in tissue gas phase formation in astronauts undergoing decompression during extravehicular activity (EVA) in microgravity. The observation may further explain the reported low incidence of DCS in space.

  5. Atmospheric chemistry of gas-phase polycyclic aromatic hydrocarbons: formation of atmospheric mutagens.

    PubMed Central

    Atkinson, R; Arey, J

    1994-01-01

    The atmospheric chemistry of the 2- to 4-ring polycyclic aromatic hydrocarbons (PAH), which exist mainly in the gas phase in the atmosphere, is discussed. The dominant loss process for the gas-phase PAH is by reaction with the hydroxyl radical, resulting in calculated lifetimes in the atmosphere of generally less than one day. The hydroxyl (OH) radical-initiated reactions and nitrate (NO3) radical-initiated reactions often lead to the formation of mutagenic nitro-PAH and other nitropolycyclic aromatic compounds, including nitrodibenzopyranones. These atmospheric reactions have a significant effect on ambient mutagenic activity, indicating that health risk assessments of combustion emissions should include atmospheric transformation products. PMID:7821285

  6. Time-dependent gas phase kinetics in a hydrogen diluted silane plasma

    NASA Astrophysics Data System (ADS)

    Nunomura, S.; Yoshida, I.; Kondo, M.

    2009-02-01

    The gas phase kinetics in a high-pressure hydrogen diluted silane plasma has been studied at time scales of 10-2-6×102 s. The time-resolved gas phase composition shows the following kinetics at different time scales: silane decomposition and polysilane generation in ≲2×10-1 s, nanoparticle formation and plasma density reduction in 10-1-100 s, polysilane accumulation in 100-102 s, and silane depletion and electrode heating in ≳101 s. Disilane radicals are implied to be the dominant film precursors in addition to silyl radicals.

  7. A microcomputer-controlled gas phase microreactor system

    SciTech Connect

    Morris, R.M.

    1983-08-01

    Although automated reactors are effective tools for studying a single type of reaction or optimizing catalyst performance, they may not be well suited for exploratory research. These reactors generally have several shortcomings. First, they may have limited versatility since they are usually designed with a single application in mind. Second, computer systems used for process control and data acquisition are often expensive and complex, so that once they are set up for a given application, it is quite difficult to adapt them for another. Because of these restrictions, experimental reactors are often operated manually, requiring a full-time operator to monitor operations and acquire data. This is a greater problem in laboratories where projects are often short-term, and the costs of setting up an automated reactor may outweigh the benefits of automation. For an automated reactor to be cost-effective in such an environment, both reactor hardware and control software must be versatile enough that they can be easily modified and adapted for different experiments. An automated gas-flow microreactor has been designed and constructed which is both inexpensive and flexible. The reactor is capable of performing three different types of experiments, 1) continuous reagent feed with analysis of the product stream, 2) pulsed-flow experiments, and 3) temperature-programmed desorption (TPD) and reaction (TPR). Conversion of the reactor from one configuration to another requires less than one hour. Process control and data acquisition are performed using an Apple II Plus microcomputer (Apple Computer Corp., Cupertino, Calif.) and an ISAAC interface device (Cyborg Corp., Newton, Mass.).

  8. Advanced indirect gas-fired heating system. Final report, August 15, 1984-June 30, 1988. Phase 2: Development. Phase 3: Application

    SciTech Connect

    Watson, J.; Bowers, J.

    1989-01-01

    In Phase II a gas-fired high-temperature regenerative radiant-tube burner system with a 'W' shaped radiant tube was developed. Phase III successfully applied that system to the Surface Combustion, Inc. 'Ultracase' furnace resulting in higher furnace temperatures, heating rates, and higher efficiencies than conventional gas-fired furnaces.

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

    NASA Astrophysics Data System (ADS)

    Sakhel, Roger R.; Sakhel, Asaad R.; Ghassib, Humam B.

    2015-12-01

    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.

  10. Self-similarity of phase-space networks of frustrated spin models and lattice gas models

    NASA Astrophysics Data System (ADS)

    Peng, Yi; Wang, Feng; Han, Yilong

    2013-03-01

    We studied the self-similar properties of the phase-spaces of two frustrated spin models and two lattice gas models. The frustrated spin models included (1) the anti-ferromagnetic Ising model on a two-dimensional triangular lattice (1a) at the ground states and (1b) above the ground states and (2) the six-vertex model. The two lattice gas models were (3) the one-dimensional lattice gas model and (4) the two-dimensional lattice gas model. The phase spaces were mapped to networks so that the fractal analysis of complex networks could be applied, i.e. the box-covering method and the cluster-growth method. These phase spaces, in turn, establish new classes of networks with unique self-similar properties. Models 1a, 2, and 3 with long-range power-law correlations in real space exhibit fractal phase spaces, while models 1b and 4 with short-range exponential correlations in real space exhibit nonfractal phase spaces. This behavior agrees with one of untested assumptions in Tsallis nonextensive statistics. Hong Kong GRC grants 601208 and 601911

  11. Photooxygenation and gas-phase reactivity of multiply threaded pseudorotaxanes.

    PubMed

    Nowosinski, Karol; Warnke, Stephan; Pagel, Kevin; Komáromy, Dávid; Jiang, Wei; Schalley, Christoph A

    2016-04-01

    The solution-phase photooxygenation of multiply threaded crown/ammonium pseudorotaxanes containing anthracene spacers is monitored by electrospray ionization Fourier-transform ion-cyclotron-resonance (ESI-FTICR) mass spectrometry. The oxygenated pseudorotaxanes are mass-selected and fragmented by infrared multiphoton dissociation (IRMPD) and/or collision-induced dissociation (CID) experiments and and their behavior compared to that of the non-oxygenated precursors. [4+2]Cycloreversion reactions lead to the loss of O2, when no other reaction channel with competitive energy demand is available. Thus, the release of molecular oxygen can serve as a reference reaction for the energy demand of other fragmentation reactions such as the dissociation of the crown/ammonium binding motifs. The photooxygenation induces curvature into the initially planar anthracene and thus significantly changes the geometry of the divalent, anthracene-spacered wheel. This is reflected in ion-mobility data. Coulomb repulsion in multiply charged pseudorotaxanes assists the oxygen loss as the re-planarization of the anthracene increases the distance between the two charges. PMID:27041657

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

    NASA Astrophysics Data System (ADS)

    Wu, Hao; Dong, Feng

    2014-04-01

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

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

    SciTech Connect

    Wu, Hao; Dong, Feng

    2014-04-11

    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.

  14. Common features in phase-space networks of frustrated spin models and lattice-gas models

    NASA Astrophysics Data System (ADS)

    Wang, Feng; Peng, Yi; Han, Yilong

    2012-02-01

    We mapped the phase spaces of the following four models into networks: (1a) the Ising antiferromagnet on triangular lattice at the ground state and (1b) above the ground state, (2) the six-vertex model (i.e. square ice or spin ice), (3) 1D lattice gas and (4) 2D lattice gas. Their phase-space networks share some common features including the Gaussian degree distribution, the Gaussian spectral density, and the small-world properties. Models 1a, 2 and 3 with long-range correlations in real space exhibit fractal phase spaces, while models 1b and 4 with short-range correlations in real space exhibit non-fractal phase spaces. This result supports one of the untested assumptions in Tsallis's non-extensive statistics.

  15. INTEGRATION OF PHOTOCATALYTIC OXIDATION WITH AIR STRIPPING OF CONTAMINATED AQUIFERS

    EPA Science Inventory

    Bench scale laboratory studies and pilot scale studies in a simulated field-test situation were performed to evaluate the integration of gas-solid ultaviolet (UV) photocatalytic oxidation (PCO) downstream if an air stripper unit as a technology for cost-effectively treating water...

  16. Real time, in situ observation of the photocatalytic inactivation of Saccharomyces cerevisiae cells.

    PubMed

    Zhang, Jingtao; Wang, Xiaoxin; Li, Qi; Shang, Jian Ku

    2015-04-01

    An in situ microscopy technique was developed to observe in real time the photocatalytic inactivation process of Saccharomyces cerevisiae (S. cerevisiae) cells by palladium-modified nitrogen-doped titanium oxide (TiON/PdO) under visible light illumination. The technique was based on building a photocatalytic micro-reactor on the sample stage of a fluorescence/phase contrast microscopy capable of simultaneously providing the optical excitation to activate the photocatalyst in the micro-reactor and the illumination to acquire phase contrast images of the cells undergoing the photocatalytic inactivation process. Using TiON/PdO as an example, the technique revealed for the first time the vacuolar activities inside S. cerevisiae cells subjected to a visible light photocatalytic inactivation. The vacuoles responded to the photocatalytic attack by the first expansion of the vacuolar volume and then contraction, before the vacuole disappeared and the cell structure collapsed. Consistent with the aggregate behavior observed from the cell culture experiments, the transition in the vacuolar volume provided clear evidence that photocatalytic disinfection of S. cerevisiae cells started with an initiation period in which cells struggled to offset the photocatalytic damage and moved rapidly after the photocatalytic damage overwhelmed the defense mechanisms of the cells against oxidative attack. PMID:25686929

  17. Sulfur doping of diamond films: Spectroscopic, electronic, and gas-phase studies

    NASA Astrophysics Data System (ADS)

    Petherbridge, James R.; May, Paul W.; Fuge, Gareth M.; Robertson, Giles F.; Rosser, Keith N.; Ashfold, Michael N. R.

    2002-03-01

    Chemical vapor deposition (CVD) has been used to grow sulfur doped diamond films on undoped Si and single crystal HPHT diamond as substrates, using a 1% CH4/H2 gas mixture with various levels of H2S addition (100-5000 ppm), using both microwave (MW) plasma enhanced CVD and hot filament (HF) CVD. The two deposition techniques yield very different results. HFCVD produces diamond films containing only trace amounts of S (as analyzed by x-ray photoelectron spectroscopy), the film crystallinity is virtually unaffected by gas phase H2S concentration, and the films remain highly resistive. In contrast, MWCVD produces diamond films with S incorporated at levels of up to 0.2%, and the amount of S incorporation is directly proportional to the H2S concentration in the gas phase. Secondary electron microscopy observations show that the crystal quality of these films reduces with increasing S incorporation. Four point probe measurements gave the room temperature resistivities of these S-doped and MW grown films as ˜200 Ω cm, which makes them ˜3 times more conductive than undoped diamond grown under similar conditions. Molecular beam mass spectrometry has been used to measure simultaneously the concentrations of the dominant gas phase species present during growth, for H2S doping levels (1000-10 000 ppm in the gas phase) in 1% CH4/H2 mixtures, and for 1% CS2/H2 gas mixtures, for both MW and HF activation. CS2 and CS have both been detected in significant concentrations in all of the MW plasmas that yield S-doped diamond films, whereas CS was not detected in the gas phase during HF growth. This suggests that CS may be an important intermediary facilitating S incorporation into diamond. Furthermore, deposition of yellow S was observed on the cold chamber walls when using H2S concentrations >5000 ppm in the MW system, but very little S deposition was observed for the HF system under similar conditions. All of these results are rationalized by a model of the important gas phase

  18. Flow field simulation of gas-water two phase flow in annular channel

    NASA Astrophysics Data System (ADS)

    Ji, Pengcheng; Dong, Feng

    2014-04-01

    The gas-water two-phase flow is very common in the industrial processes. the deep understanding of the two-phase flow state is to achieve the production equipment design and safe operation. In the measurement of gas-water two-phase flow, the differential pressure sensor is widely used, and some measurement model of multiphase flow have been concluded. The differential pressure is generated when fluid flowing through the throttling components to calculate flow rate. This paper mainly focuses on two points: 1. The change rule of the parameters include velocity, pressure, phase fraction as the change of time, when the phase inlet velocity is given. 2. Analysis the distribution of the parameters above-mentioned at a certain moment under the condition of different water inlet velocity. Three-dimensional computational fluid dynamics (CFD) approach was used to simulate gas-water two-phase flow fluid in the annular channel, which is composed of horizontal pipe and long- waist cone sensor. The simulation results were obtained from FLUENT software.

  19. Quantitative Fourier transform infrared analysis of gas phase cigarette smoke and other gas mixtures

    SciTech Connect

    Cueto, R.; Church, D.F.; Pryor, W.A. )

    1989-03-01

    A new method for the analysis of selected components in complex gas mixtures has been developed utilizing a relatively inexpensive Fourier transform infrared spectrometer and a continuous flow gas cell. The method was used to monitor nitric oxide and nitrogen dioxide concentrations in cigarette smoke with time. Using multivariate least-square regression analysis, it is possible to simultaneously quantitate both NO and NO{sub 2}, even in the presence of overlapping peaks. Using this method, the oxidation of nitric oxide in the presence of isoprene in cigarette smoke and in a model system was followed with time. The method also can be applied to other compounds in smoke or to any other gaseous mixture.

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

    SciTech Connect

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

    2009-02-01

    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. Photocatalytic reactions of nanocomposite of ZnS nanoparticles and montmorillonite

    NASA Astrophysics Data System (ADS)

    Praus, P.; Reli, M.; Kočí, K.; Obalová, L.

    2013-06-01

    ZnS nanoparticles stabilized by cetyltrimethylammonium bromide (CTAB) were deposited on montmorillonite (MMT) forming a ZnS-CTA-MMT nanocomposite. The nanocomposite was characterized by scanning electron microscopy (SEM), Fourier transformed infrared (FTIR) and UV diffuse reflectance spectra (DRS) spectrometry, X-ray powder diffraction (XRD) and specific surface area measurements. Thereafter, it was used for photocatalytic reactions under UV irradiation (Hg lamp) in three different reaction media with different pH: NaOH solution, HCl solution and water. Prior to the photocatalytic reactions the dispersions were saturated by carbon dioxide to buffer the systems. The main reaction products in gas phase determined by gas chromatography were hydrogen and methane. The reactions were monitored by measuring oxidation-reduction potentials. The highest yields of hydrogen were obtained in the dispersion acidified by HCl but the concentrations of methane were similar in all tested media. Hydrogen was supposed to be formed by the reaction of two hydrogen radicals. Methane was formed by the reduction of carbon dioxide and by the partial decomposition of CTAB.

  2. Study on photocatalytic degradation of several volatile organic compounds.

    PubMed

    Zuo, Guo-Min; Cheng, Zhen-Xing; Chen, Hong; Li, Guo-Wen; Miao, Ting

    2006-02-01

    The gas-phase photolytic and photocatalytic reactions of several aromatics and chlorohydrocarbons were investigated. The experimental results revealed that chlorohydrocarbons like trichloroethylene, dichloromethane and chloroform could be degraded through either photolysis or photocatalysis under irradiation of germicidal lamp, and the elimination rate of chlorohydrocarbons through photolysis was quicker than that through photocatalysis. UV light from a germicidal lamp could directly lead to degradation of toluene but could hardly act on benzene. The photodegradation rate for these volatile organic compounds (VOCs) through photolysis followed an order: trichloroethylene>chloroform>dichloromethane>toluene>benzene>carbon tetrachloride, and through photocatalysis followed: trichloroethylene>chloroform>toluene>dichloromethane>benzene>carbon tetrachloride. Besides, a series of modified TiO2 photocatalysts were prepared by depositing noble metal, doping with transition metal ion, recombining with metal oxides and modifying with super strong acid. Activity of these catalysts was examined upon photocatalytic degradation of benzene as a typical compound that was hard to be degraded. It indicated that these modification methods could promote the activity of TiO2 catalyst to different extent. The apparent zero-order reaction rate constant for degrading benzene over SnO2/TiO2 catalyst had the highest value, which was nearly three times as that over P25 TiO2. But it simultaneously had the lowest rate for mineralizing the objective compound. In spite that Fe3+/TiO2 catalyst behaved slightly less active than SnO2/TiO2 for degradation of benzene, the mineralization rate over Fe3+/TiO2 was the highest one among the prepared catalysts. PMID:16157448

  3. Fizzy Extraction of Volatile and Semivolatile Compounds into the Gas Phase.

    PubMed

    Chang, Cheng-Hao; Urban, Pawel L

    2016-09-01

    Extraction of volatile and semivolatile compounds from liquid matrixes with high yields, and transferring the extracts to detectors in real time, is challenging. Common extraction procedures involve heating the samples to release the analytes to the gas phase and, in some cases, trapping the gas-phase analytes into sorbents or containers. Here, we propose a new method for fast extraction of volatile and semivolatile compounds from liquid matrixes. This method involves dissolution of a carrier gas in the liquid sample by applying a moderate overpressure (∼150 kPa) and stirring the sample. An abrupt decompression of the extraction chamber leads to effervescence. In this step, many bubbles are instantly formed in the sample matrix. The dissolved carrier gas as well as dissolved volatiles are liberated into the headspace of the extraction chamber within a short period of time (few seconds). The gaseous effluent of the extraction chamber is immediately transferred to the online detector; in this case, an atmospheric pressure chemical ionization interface of a triple quadrupole mass spectrometer. The fast release of the gas-phase extract gives rise to a high signal recorded by the detector; several times higher than the signal recorded during direct infusion of headspace vapors without fizzy extraction. This feature provides the means to detect and quantify analytes present in solutions in a short period of time. Here we show that fizzy extraction is suitable for analysis of volatile/semivolatile compounds present in various samples, including those containing complex matrixes. PMID:27504910

  4. A modeling and experimental study of flue gas desulfurization in a dense phase tower.

    PubMed

    Chang, Guanqin; Song, Cunyi; Wang, Li

    2011-05-15

    We used a dense phase tower as the reactor in a novel semi-dry flue gas desulfurization process to achieve a high desulfurization efficiency of over 95% when the Ca/S molar ratio reaches 1.3. Pilot-scale experiments were conducted for choosing the parameters of the full-scale reactor. Results show that with an increase in the flue gas flow rate the rate of the pressure drop in the dense phase tower also increases, however, the rate of the temperature drop decreases in the non-load hot gas. We chose a water flow rate of 0.6 kg/min to minimize the approach to adiabatic saturation temperature difference and maximize the desulfurization efficiency. To study the flue gas characteristics under different processing parameters, we simulated the desulfurization process in the reactor. The simulated data matched very well with the experimental data. We also found that with an increase in the Ca/S molar ratio, the differences between the simulation and experimental data tend to decrease; conversely, an increase in the flue gas flow rate increases the difference; this may be associated with the surface reactions caused by collision, coalescence and fragmentation between the dispersed phases. PMID:21377795

  5. Effect of surfactants on gas holdup of two-phase bubble columns

    SciTech Connect

    Estevez, L.A. ); Saez, E.; Pachino, J.; Cavicchioli, I. )

    1988-01-01

    Two-phase experiments have been carried out using organic liquids with a surfactant and air in a bubble column 30 (cm) inside diameter and 3 (m) tall. Under the presence of the surfactant, two distinct regions are observed: a bubbling region is the lower part, and a froth zone in the upper part of the column. Intrinsic gas holdups were measured in each region. Results showed that intrinsic gas holdup did not change significantly with surfactant concentration. However, the position of the limiting surface separating the two regions varied considerably with surfactant concentration, thus affecting strongly the overall gas holdup. Based on the described experimental observations, correlations for intrinsic and overall gas holdups have been proposed. Intrinsic gas holdups have been correlated and a function of gas and liquid superficial velocities, and not as functions of surfactant concentration. Overall gas holdups have been expressed in terms of intrinsic gas holdup and of the fraction PHI of the column that is occupied by the froth region. The variable PHI is the one that has been correlated in terms of the surfactant concentration.

  6. Visible Light-Driven Photocatalytic Activity of Oleic Acid-Coated TiO2 Nanoparticles Synthesized from Absolute Ethanol Solution

    NASA Astrophysics Data System (ADS)

    Li, Huihui; Liu, Bin; Yin, Shu; Sato, Tsugio; Wang, Yuhua

    2015-10-01

    The one-step synthesis of oleic acid-coated TiO2 nanoparticles with visible light-driven photocatalytic activity was reported by this manuscript, using oleic acid-ethanol as crucial starting materials. The photocatalytic degradation of nitrogen monoxide (deNOx) in the gas phase was investigated in a continuous reactor using a series of TiO2 semiconductors, prepared from oleic acid- or acetic acid-ethanol solution. The surface modification on TiO2 by organic fatty acid, oleic acid, could reinvest TiO2 photocatalyst with the excellent visible light response. The deNOx ability is almost as high as 30 % destruction in the visible light region ( λ > 510 nm) which is similar to the nitrogen-doped TiO2. Meanwhile, acetic acid, a monobasic acid, has a weaker ability on visible light modification of TiO2.

  7. Gas and grain chemical composition in cold cores as predicted by the Nautilus 3-phase model

    NASA Astrophysics Data System (ADS)

    Ruaud, Maxime; Wakelam, Valentine; Hersant, Franck

    2016-04-01

    We present an extended version of the 2-phase gas-grain code NAUTILUS to the 3-phase modelling of gas and grain chemistry of cold cores. In this model, both the mantle and the surface are considered as chemically active. We also take into account the competition among reaction, diffusion and evaporation. The model predictions are confronted to ice observations in the envelope of low-mass and massive young stellar objects as well as toward background stars. Modelled gas-phase abundances are compared to species observed toward TMC-1 (CP) and L134N dark clouds. We find that our model successfully reproduces the observed ice species. It is found that the reaction-diffusion competition strongly enhances reactions with barriers and more specifically reactions with H2, which is abundant on grains. This finding highlights the importance to have a good approach to determine the abundance of H2 on grains. Consequently, it is found that the major N-bearing species on grains go from NH3 to N2 and HCN when the reaction-diffusion competition is accounted. In the gas-phase and before few 105 yrs, we find that the 3-phase model does not have a strong impact on the observed species compared to the 2-phase model. After this time, the computed abundances dramatically decrease due to the strong accretion on dust, which is not counterbalanced by the desorption less efficient than in the 2-phase model. This strongly constrains the chemical-age of cold cores to be of the order of few 105 yrs.

  8. SPECIATION OF GAS-PHASE AND FINE PARTICLE EMISSIONS FROM BURNING OF FOLIAR FUELS: JOURNAL ARTICLE

    EPA Science Inventory

    NRMRL-RTP-P- 620 Hays**, M.D., Geron*, C.D., Linna**, K.J., Smith*, N.D., and Schauer, J.J. Speciation of Gas-Phase and Fine Particle Emissions from Burning of Foliar Fuels. Submitted to: Environmental Science & Technology EPA/600/J-02/234, http://pubs.acs.org/journals/esthag/...

  9. Ozonation of coal vitrinites of different metamorphism degrees in gas and liquid phases

    SciTech Connect

    S.A. Semenova; Y.F. Patrakov

    2007-02-15

    The comparative analysis of the dynamics of accumulation of oxygen-containing groups in coals of different metamorphism degrees under their ozonation in the gas phase and in chloroform has been performed. The coals of the middle stage of metamorphism demonstrate the highest reactivity. The ozonation in chloroform proceeds with a higher intensity.

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

    PubMed

    Zhu, Hongying; Huang, Guangming

    2015-03-31

    In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages. PMID:25813029

  11. CONTINUOUS STIRRED TANK REACTOR INVESTIGATION OF THE GAS-PHASE REACTION OF HYDROXYL RADICALS AND TOLUENE

    EPA Science Inventory

    A continuous stirred tank reactor (CSTR) was used to study the gas phase reaction between HO and toluene. HO was generated by the in situ photolysis of nitrous acid. Flow reactor operation at steady state conditions with a residence time of 20 minutes allowed investigation of pri...

  12. EFFECTS OF RING STRAIN ON GAS-PHASE RATE CONSTANTS. 2. OH RADICAL REACTIONS WITH CYCLOALKENES

    EPA Science Inventory

    Relative rate constants for the gas phase reactions of OH radicals with a series of cycloalkenes have been determined at 298 + or - 2 K, using methyl nitrite photolysis in air as a source of OH radicals. The data show that the rate constants for the nonconjugated cycloalkenes stu...

  13. Probing aerosol formation by comprehensive measurements of gas phase oxidation products

    NASA Astrophysics Data System (ADS)

    Ehn, Mikael; Kleist, Einhard; Junninen, Heikki; Sipilä, Mikko; Petäjä, Tuukka; Pullinen, Iida; Springer, Monika; Andres, Stefanie; Rissanen, Matti; Kontkanen, Jenni; Schobesberger, Siegfried; Rubach, Florian; Tillman, Ralf; Lee, Ben H.; Lopez-Hilfiker, Felipe; Kerminen, Veli-Matti; Kulmala, Markku; Worsnop, Douglas R.; Thornton, Joel; Wildt, Jürgen; Mentel, Thomas F.

    2013-05-01

    A comprehensive suite of chemical ionization mass spectrometers (CIMS) were deployed for chamber studies of monoterpene oxidation. The CIMS instruments were able to detect several different groups of compounds ranging from volatile to practically non-volatile. The compound groups showed very different behavior and correlations with aerosol number and mass. Results suggest that major gas phase contributors are not considered in current models.

  14. A Lithium Amide Protected Against Protonation in the Gas Phase: Unexpected Effect of LiCl.

    PubMed

    Lesage, Denis; Barozzino-Consiglio, Gabriella; Duwald, Romain; Fressigné, Catherine; Harrison-Marchand, Anne; Faull, Kym F; Maddaluno, Jacques; Gimbert, Yves

    2015-06-19

    In cold THF and in the presence of LiCl, a lithium pyrrolidinylamide forms a 1:1 mixed aggregate, which is observed directly by ESI-MS. Gas-phase protonation of this species leads to selective transfer of H(+) to the chlorine, suggesting that LiCl shields the amide nitrogen and prevents its direct protonation. PMID:25997158

  15. CHEMICAL TRANSFORMATION MODULES FOR EULERIAN ACID DEPOSITION MODELS. VOLUME 1. THE GAS-PHASE CHEMISTRY

    EPA Science Inventory

    This study focuses on the review and evaluation of mechanistic and kinetic data for the gas-phase reactions that lead to the production of acidic substances in the environment. A master mechanism is designed that treats oxides, sulfur dioxide, ozone, hydrogen peroxide, ammonia, t...

  16. ADVANCED OXIDATION AND REDUCTION PROCESSES IN THE GAS PHASE USING NON-THERMAL PLASMAS

    EPA Science Inventory

    In the past several years interest in gas-phase pollution control has increased, arising from a larger body of regulations and greater respect for the environment. Advanced oxidation technologies (AOTs), historically used to treat recalcitrant water pollutants via hydroxyl-radica...

  17. ECO LOGIC INTERNATIONAL GAS-PHASE CHEMICAL REDUCTION PROCESS - THE THERMAL DESORPTION UNIT - APPLICATIONS ANALYSIS REPORT

    EPA Science Inventory

    ELI ECO Logic International, Inc.'s Thermal Desorption Unit (TDU) is specifically designed for use with Eco Logic's Gas Phase Chemical Reduction Process. The technology uses an externally heated bath of molten tin in a hydrogen atmosphere to desorb hazardous organic compounds fro...

  18. Bond-Specific Dissociation Following Excitation Energy Transfer for Distance Constraint Determination in the Gas Phase

    PubMed Central

    2015-01-01

    Herein, we report chemistry that enables excitation energy transfer (EET) to be accurately measured via action spectroscopy on gaseous ions in an ion trap. It is demonstrated that EET between tryptophan or tyrosine and a disulfide bond leads to excited state, homolytic fragmentation of the disulfide bond. This phenomenon exhibits a tight distance dependence, which is consistent with Dexter exchange transfer. The extent of fragmentation of the disulfide bond can be used to determine the distance between the chromophore and disulfide bond. The chemistry is well suited for the examination of protein structure in the gas phase because native amino acids can serve as the donor/acceptor moieties. Furthermore, both tyrosine and tryptophan exhibit unique action spectra, meaning that the identity of the donating chromophore can be easily determined in addition to the distance between donor/acceptor. Application of the method to the Trpcage miniprotein reveals distance constraints that are consistent with a native-like fold for the +2 charge state in the gas phase. This structure is stabilized by several salt bridges, which have also been observed to be important previously in proteins that retain native-like structures in the gas phase. The ability of this method to measure specific distance constraints, potentially at numerous positions if combined with site-directed mutagenesis, significantly enhances our ability to examine protein structure in the gas phase. PMID:25174489

  19. Bond-specific dissociation following excitation energy transfer for distance constraint determination in the gas phase.

    PubMed

    Hendricks, Nathan G; Lareau, Nichole M; Stow, Sarah M; McLean, John A; Julian, Ryan R

    2014-09-24

    Herein, we report chemistry that enables excitation energy transfer (EET) to be accurately measured via action spectroscopy on gaseous ions in an ion trap. It is demonstrated that EET between tryptophan or tyrosine and a disulfide bond leads to excited state, homolytic fragmentation of the disulfide bond. This phenomenon exhibits a tight distance dependence, which is consistent with Dexter exchange transfer. The extent of fragmentation of the disulfide bond can be used to determine the distance between the chromophore and disulfide bond. The chemistry is well suited for the examination of protein structure in the gas phase because native amino acids can serve as the donor/acceptor moieties. Furthermore, both tyrosine and tryptophan exhibit unique action spectra, meaning that the identity of the donating chromophore can be easily determined in addition to the distance between donor/acceptor. Application of the method to the Trpcage miniprotein reveals distance constraints that are consistent with a native-like fold for the +2 charge state in the gas phase. This structure is stabilized by several salt bridges, which have also been observed to be important previously in proteins that retain native-like structures in the gas phase. The ability of this method to measure specific distance constraints, potentially at numerous positions if combined with site-directed mutagenesis, significantly enhances our ability to examine protein structure in the gas phase. PMID:25174489

  20. SPECIATION OF GAS-PHASE AND FINE PARTICLE EMISSIONS FROM BURNING OF FOLIAR FUELS

    EPA Science Inventory

    Particle size distributions (10-1000 nm aerodynamic diameter), physical and chemical properties of fine particle matter (PM2.5) with aerodynamic diameter <2.5 micrometers, and gas-phase emissions from controlled open burning of assorted taxa were measured. Chemical speciation of ...

  1. Methylation of 2-Naphthol Using Dimethyl Carbonate under Continuous-Flow Gas-Phase Conditions

    ERIC Educational Resources Information Center

    Tundo, Pietro; Rosamilia, Anthony E.; Arico, Fabio

    2010-01-01

    This experiment investigates the methylation of 2-naphthol with dimethyl carbonate. The volatility of the substrates, products, and co-products allows the reaction to be performed using a continuous-flow gas-phase setup at ambient pressure. The reaction uses catalytic quantities of base, achieves high conversion, produces little waste, and…

  2. Gas phase regioselectivity in the deprotonation of p-cresol radical cation

    NASA Astrophysics Data System (ADS)

    Chiavarino, B.; Crestoni, M. E.; Fornarini, S.

    2003-04-01

    The deprotonation of the radical cation of p-cresol, a model of tyrosine residues, has been studied kinetically in the gas phase. The reaction has revealed the operation of competitive deprotonation sites depending on the strength of the base, as shown by an FT-ICR study using d-labelling.

  3. Planar gas chromatography column on aluminum plate with multi-walled carbon nanotubes as stationary phase

    NASA Astrophysics Data System (ADS)

    Platonov, I. A.; Platonov, V. I.; Pavelyev, V. S.

    2016-04-01

    The high selectivity of the adsorption layer for low-boiling alkanes is shown, the separation factor (α) couple iso-butane / butane is 1.9 at a column temperature of 50 °C.The paper presents sorption and selective properties of planar gas chromatography column on aluminum plate with multi-walled carbon nanotubes as the stationary phase.

  4. Chemical studies of elements with Z ⩾ 104 in gas phase

    NASA Astrophysics Data System (ADS)

    Türler, Andreas; Eichler, Robert; Yakushev, Alexander

    2015-12-01

    Chemical investigations of superheavy elements in the gas-phase, i.e. elements with Z ≥ 104, allow assessing the influence of relativistic effects on their chemical properties. Furthermore, for some superheavy elements and their compounds quite unique gas-phase chemical properties were predicted. The experimental verification of these properties yields supporting evidence for a firm assignment of the atomic number. Prominent examples are the high volatility observed for HsO4 or the very weak interaction of Cn with gold surfaces. The unique properties of HsO4 were exploited to discover the doubly-magic even-even nucleus 270Hs and the new isotope 271Hs. The combination of kinematic pre-separation and gas-phase chemistry allowed gaining access to a new class of relatively fragile compounds, the carbonyl complexes of elements Sg through Mt. A not yet resolved issue concerns the interaction of Fl with gold surfaces. While competing experiments agree on the fact that Fl is a volatile element, there are discrepancies concerning its adsorption on gold surfaces with respect to its daughter Cn. The elucidation of these and other questions amounts to the fascination that gas-phase chemical investigations exert on current research at the extreme limits of chemistry today.

  5. SELECTIVE OXIDATION OF ALCOHOLS IN GAS PHASE USING LIGHT-ACTIVATED TITANIUM DIOXIDE

    EPA Science Inventory

    Selective oxidations of various primary and secondary alcohols were studied in a gas phase photochemical reactor using immobilized TiO2 catalyst. An annular photoreactor was used at 463K with an average contact time of 32sec. The system was found to be specifically suited for the...

  6. Thermodynamics and kinetics of gas-phase reactions in the Ti-Cl-H system

    SciTech Connect

    Teyssandier, F.; Allendorf, M.D.

    1998-06-01

    A mechanism and associated rate constants for the gas-phase chemical reactions that occur during the chemical vapor deposition (CVD) of titanium from titanium tetrachloride (TiCl{sub 4})/hydrogen mixtures is presented. TiCl{sub 4} is the most widely used inorganic precursor employed in the CVD of titanium-containing materials, such as titanium nitride, titanium carbide, and titanium diboride. In this work, rate constants for the unimolecular decomposition reactions of the titanium chlorides were predicted using Rice-Ramsberger-Kassel-Marcus theory for unimolecular reaction, while the rate constants for bimolecular reactions between TiCl{sub n} species and hydrogen atoms were estimated using an empirical correlation. Calculations at thermodynamic equilibrium over a range of temperatures and total pressures characteristic of Ti CVD conditions are presented first. The time-dependent evolution of the gas-phase composition is then simulated using the proposed mechanism. The results suggest that equilibrium predictions of gas-phase concentrations should be a good approximation at 1,500 K, unless very short residence times and low pressures are involved. In contrast, equilibrium calculations do not accurately reflect the gas-phase composition at 1,000 K.

  7. GAS-PHASE OXIDATION PRODUCTS OF BIPHENYL AND POLYCHLORINATED BIPHENYLS (R825377)

    EPA Science Inventory

    Our laboratory recently measured the gas-phase reaction rate constants of
    polychlorinated biphenyls (PCBs) with the hydroxyl radical (OH) and concluded
    that OH reactions are the primary removal pathway of PCBs from the atmosphere.
    With the reaction system previousl...

  8. OH REACTION KINETICS OF GAS-PHASE A- AND G-HEXACHLOROCYCLOHEXANE AND HEXACHLOROBENZENE. (R825377)

    EPA Science Inventory

    Rate constants for the gas-phase reactions of the hydroxyl
    radical (OH) with - and -hexachlorocyclohexane (-
    and CONTROL OF UTILITY BOILER AND GAS TURBINE POLLUTANT EMISSIONS BY COMBUSTION MODIFICATION--PHASE II

    EPA Science Inventory

    The report gives results of Phase II of a field study to assess the applicability of combustion modification (CM) techniques to control NOx and other pollutant emissions from utility boilers and gas turbines without causing deleterious side effects. Comprehensive, statistically d...

  9. Gas-phase reaction study of disilane pyrolysis: Applications to low pressure chemical vapor deposition

    SciTech Connect

    Johannes, J.E.; Ekerdt, J.G. . Dept. of Chemical Engineering)

    1994-08-01

    The gas-phase thermal reactions during disilane decomposition at low pressure chemical vapor deposition conditions were studied from 300 to 1,000 K using resonance enhanced multiphoton ionization (REMPI) and multiphoton ionization (MPI). REMPI of gas-phase Si, mass 28, was detected from 640 to 840 K and 1 to 10 Torr, with a maximum signal intensity between 700 to 720 K. During disilane decomposition, no SiH (427.8 nm), SiH[sub 2] (494-515 nm), or SiH[sub 3] (419.0 nm) was detected. MPI of higher silanes, silenes, and silylenes were detected through mass fragments 2, 32, and 60; these species reached a maximum signal intensity 20 degrees prior to the mass-28 maximum. Modeling studies that included a detailed low pressure gas-phase kinetic scheme predict relative gas-phase partial pressures generated during disilane pyrolysis. The model predicted experimental trends in the Si partial pressure and the higher silane, silene, and silylene partial pressures.

  10. Theoretical Study of the Pyrolysis of Methyltrichlorosilane in the Gas Phase. 1.Thermodynamics

    SciTech Connect

    Ge, Yingbin; Gordon, Mark S.; Battaglia, Francine; Fox, Rodney O.

    2007-03-01

    Structures and energies of the gas-phase species produced during and after the various unimolecular decomposition reactions of methyltrichlorosilane (MTS) with the presence of H2 carrier gas were determined using second-order perturbation theory (MP2). Single point energies were obtained using singles + doubles coupled cluster theory, augmented by perturbative triples, CCSD(T). Partition functions were obtained using the harmonic oscillator-rigid rotor approximation. A 114-reaction mechanism is proposed to account for the gas-phase chemistry of MTS decompositions. Reaction enthalpies, entropies, and Gibbs free energies for these reactions were obtained at 11 temperatures ranging from 0 to 2000 K including room temperature and typical chemical vapor deposition (CVD) temperatures. Calculated and experimental thermodynamic properties such as heat capacities and entropies of various species and reaction enthalpies are compared, and theory is found to provide good agreement with experiment.

  11. Onset conditions for gas phase reaction and nucleation in the CVD of transition metal oxides

    NASA Technical Reports Server (NTRS)

    Collins, J.; Rosner, D. E.; Castillo, J.

    1992-01-01

    A combined experimental/theoretical study is presented of the onset conditions for gas phase reaction and particle nucleation in hot substrate/cold gas CVD of transition metal oxides. Homogeneous reaction onset conditions are predicted using a simple high activation energy reacting gas film theory. Experimental tests of the basic theory are underway using an axisymmetric impinging jet CVD reactor. No vapor phase ignition has yet been observed in the TiCl4/O2 system under accessible operating conditions (below substrate temperature Tw = 1700 K). The goal of this research is to provide CVD reactor design and operation guidelines for achieving acceptable deposit microstructures at the maximum deposition rate while simultaneously avoiding homogeneous reaction/nucleation and diffusional limitations.

  12. Chemical mechanisms of photocatalytic de-soiling and de-polluting processes in indoor environments and urban surfaces

    NASA Astrophysics Data System (ADS)

    Sleiman, M.; Rosseler, O.; Montesinos, N.; Litter, M.; Bikiel, D.; Kirchstetter, T.; Bluhm, H.; Ahmed, M.; Salmeron, M.; Destaillats, H.

    2013-12-01

    Photocatalysis has been postulated as a promising approach for the de-pollution of indoor air and urban atmospheres, and for self-cleaning surfaces. Building materials and coatings containing nano-sized TiO2 photocatalytic functionalities are gaining market share, including self-cleaning building envelope materials (coatings, mortar, plaster, architectural fabrics and tiles) and indoor air purifiers. While many studies have reported good performance of photocatalysis in the removal of organic pollutants from indoor air, more information is needed to understand secondary emissions of potentially harmful byproducts from photocatalytic air cleaners. This presentation will describe analytical methods and experimental results from room-sized chamber experiments using a realistic challenge VOC mixture at low ppb levels. We will also present results from separate studies that used synchrotron-based surface spectroscopic and mass spectrometric methods to better understand the photocatalytic mechanisms that regulate the de-soiling and de-polluting activity. Two photocatalytic processes were studied: de-noxification (NOx removal) and de-soiling (removal of deposited black carbon or soot). Ambient pressure XPS was used to study surface and gas-phase species formed during adsorption of NO2 on TiO2 and subsequent UV irradiation at λ = 365 nm. The results illustrate how NOx chemistry on TiO2 surfaces can be affected by the presence of water vapor, heteroatoms present as impurities, and carbonaceous soiling. The reactivity of NOx and NO3- on surfaces leads to reduced adsorbed and gas-phase nitrogenated species. These processes need to be considered in the engineering of depolluting materials and incorporated into atmospheric models. De-soiling properties were investigated by analyzing soot oxidation on TiO2 surfaces. Model soot samples were used as surrogates of urban grime. Using laser desorption coupled with time-of-flight (TOF) mass spectrometry synchrotron ionization, we

  13. Chemometric study of retention on binary stationary phases in gas chromatography.

    PubMed

    Bouzouane, S; Righezza, M; Touabet, A

    2012-02-01

    Using gas chromatography, data analysis is performed on a dataset consisting of 486 retention indices, 27 standards (ramified alkanes, aliphatic alcohols, and aromatic compounds), 6 pure and binary stationary phases, and three temperatures. The behavior of the pure stationary phases (OV-3, OV-225, OV-61-OH, and OV-1701-OH) and the binary stationary phases (OV-3/OV-225 and OV-61-OH/OV-1701-OH) at different temperatures (60°C-100°C) is investigated with factor and topological analysis. The influence of temperature and the nature of the mixed stationary phases on the retention indices is studied by correspondence factor analysis (CFA). The non-additivity of the retention properties of the pure phases used as mixed phases is clearly established by CFA. The topological analysis of the substituent's effect is investigated with a DARC/PELCO procedure and shows the particular influence of the stationary phase composition on the retention. The substituent effect is measured for the pure and binary stationary phases at various temperatures. The evolution of the substituent effect from the pure stationary phases to the binary phases is discussed. PMID:22298764

  14. Are ionic liquids pairwise in gas phase? A cluster approach and in situ IR study.

    PubMed

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

    2013-04-28

    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. PMID:23493905

  15. Lattice model theory of the equation of state covering the gas, liquid, and solid phases

    NASA Technical Reports Server (NTRS)

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

    1975-01-01

    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.

  16. Impact of Gas-liquid Two-phase Flow on Fluid Borne Noise

    NASA Astrophysics Data System (ADS)

    Taniwaki, Mitsuhiro; Shimomura, Nobuo

    In pipe lines such as those found in refrigeration cycle, a gas-liquid two-phase flow may occur because of a pressure change in the pipe. This flow causes noise. A vapor phase ratio in a fluid and the behavior of bubbles are related to the outbreak of noise. This experimental study investigated the fluid borne noise caused by gas-liquid two-phase flow passing through a contracted section in horizontal pipe. In the experiment, sound pressure was measured for two purposes: to see the influence of the air-water ratio on sound pressure and to see the change in sound pressure when a single bubble passed through a contracted section in horizontal pipe. The experiment showed that the fluid borne noise of gas-liquid two-phase flow grew louder than that of a liquid single-phase flow. As for the frequency distribution of the fluid borne noise, the sound pressure level was higher in the high frequency band. Furthermore, the fluid borne noise grew louder with increasing bubble diameter.

  17. Gas-Phase Oxidation, Particle Uptake, and Product Studies of Isoprene Epoxydiols

    NASA Astrophysics Data System (ADS)

    Bates, K. H.; Nguyen, T. B.; St Clair, J. M.; Crounse, J.; Zhang, X.; Coggon, M.; Schwantes, R.; Bennett, N.; Stoltz, B.; Wennberg, P. O.; Seinfeld, J.

    2013-12-01

    Isoprene epoxydiols (IEPOX), discovered in 2009 as low-NOx atmospheric oxidation products of the ubiquitous biogenic precursor isoprene, are key intermediates in the formation of secondary organic aerosol (SOA) from biogenic emissions. Recent studies carried out in the Caltech environmental chambers have elucidated the gas-phase OH oxidation rates and products, particle uptake rates, and particle-phase OH oxidation products of three isomers of IEPOX synthesized in-house. Gas-phase oxidation studies were conducted in 1 m3 chambers at both high- and low-NOx conditions, and were monitored by GC-FID, two types of chemical ionization mass spectrometry (CIMS), and GC-CIMS. Comparisons with previous studies on isoprene showed that the two β-IEPOX isomers dominate over the ∂ isomers under atmospheric conditions, and the use of propene as an internal standard provided a robust estimate of OH oxidation rates between 0.99*10-11 and 1.67*10-11 cm3molec-1s-1 for the three isomers. Particle uptake and oxidation studies were conducted in 28 m3 chambers, and were monitored by GC-FID, CIMS, an aerosol mass spectrometer (AMS), and a differential mobility analyzer (DMA). Particle uptake showed a strong dependence on humidity, with no uptake on dry seed, and was faster on ammonium sulfate seed than sodium chloride seed. Particle-phase oxidation gave similar products to gas-phase oxidation by OH radicals.

  18. Roaming-mediated ultrafast isomerization of geminal tri-bromides in the gas and liquid phases

    NASA Astrophysics Data System (ADS)

    Mereshchenko, Andrey S.; Butaeva, Evgeniia V.; Borin, Veniamin A.; Eyzips, Anna; Tarnovsky, Alexander N.

    2015-07-01

    ‘Roaming’ is a new and unusual class of reaction mechanism that has recently been discovered in unimolecular dissociation reactions of isolated molecules in the gas phase. It is characterized by frustrated bond cleavage, after which the two incipient fragments ‘roam’ on a flat region of the potential energy surface before reacting with one another. Here, we provide evidence that supports roaming in the liquid phase. We are now able to explain previous solution-phase experiments by comparing them with new ultrafast transient absorption data showing the photoisomerization of gas-phase CHBr3. We see that, upon S0-S1 excitation, gas-phase CHBr3 isomerizes within 100 fs into the BrHCBr-Br species, which is identical to what has been observed in solution. Similar sub-100 fs isomerization is now also observed for BBr3 and PBr3 in solution upon S1 excitation. Quantum chemical simulations of XBr3 (X = B, P or CH) suggest that photochemical reactivity in all three cases studied is governed by S1/S0 conical intersections and can best be described as occurring through roaming-mediated pathways.

  19. Roaming-mediated ultrafast isomerization of geminal tri-bromides in the gas and liquid phases.

    PubMed

    Mereshchenko, Andrey S; Butaeva, Evgeniia V; Borin, Veniamin A; Eyzips, Anna; Tarnovsky, Alexander N

    2015-07-01

    'Roaming' is a new and unusual class of reaction mechanism that has recently been discovered in unimolecular dissociation reactions of isolated molecules in the gas phase. It is characterized by frustrated bond cleavage, after which the two incipient fragments 'roam' on a flat region of the potential energy surface before reacting with one another. Here, we provide evidence that supports roaming in the liquid phase. We are now able to explain previous solution-phase experiments by comparing them with new ultrafast transient absorption data showing the photoisomerization of gas-phase CHBr3. We see that, upon S0-S1 excitation, gas-phase CHBr3 isomerizes within 100 fs into the BrHCBr-Br species, which is identical to what has been observed in solution. Similar sub-100 fs isomerization is now also observed for BBr3 and PBr3 in solution upon S1 excitation. Quantum chemical simulations of XBr3 (X = B, P or CH) suggest that photochemical reactivity in all three cases studied is governed by S1/S0 conical intersections and can best be described as occurring through roaming-mediated pathways. PMID:26100804

  1. Product energy deposition of CN + alkane H abstraction reactions in gas and solution phases

    NASA Astrophysics Data System (ADS)

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

    2011-06-01

    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.

  2. Quantification of Conventional and Nonconventional Charge-Assisted Hydrogen Bonds in the Condensed and Gas Phases.

    PubMed

    Katsyuba, Sergey A; Vener, Mikhail V; Zvereva, Elena E; Fei, Zhaofu; Scopelliti, Rosario; Brandenburg, Jan Gerit; Siankevich, Sviatlana; Dyson, Paul J

    2015-11-01

    Charge-assisted hydrogen bonds (CAHBs) play critical roles in many systems from biology through to materials. In none of these areas has the role and function of CAHBs been explored satisfactorily because of the lack of data on the energy of CAHBs in the condensed phases. We have, for the first time, quantified three types of CAHBs in both the condensed and gas phases for 1-(2'-hydroxylethyl)-3-methylimidazolium acetate ([C2OHmim][OAc]). The energy of conventional OH···[OAc](-) CAHBs is ∼10 kcal·mol(-1), whereas nonconventional C(sp2)H···[OAc](-) and C(sp3)H···[OAc](-) CAHBs are weaker by ∼5-7 kcal·mol(-1). In the gas phase, the strength of the nonconventional CAHBs is doubled, whereas the conventional CAHBs are strengthened by <20%. The influence of cooperativity effects on the ability of the [OAc](-) anion to deprotonate the imidazolium cation is evaluated. The ability to quantify CAHBs in the condensed phase on the basis of easier accessible gas-phase estimates is highlighted. PMID:26496074

  3. Compilation and evaluation of gas-phase diffusion coefficients of reactive trace gases in the atmosphere: volume 2. Organic compounds and Knudsen numbers for gas uptake calculations

    NASA Astrophysics Data System (ADS)

    Tang, M. J.; Shiraiwa, M.; Pöschl, U.; Cox, R. A.; Kalberer, M.

    2015-02-01

    Diffusion of organic vapours to the surface of aerosol or cloud particles is an important step for the formation and transformation of atmospheric particles. So far, however, a database of gas phase diffusion coefficients for organic compounds of atmospheric interest has not been available. In this work we have compiled and evaluated gas phase diffusivities (pressure-independent diffusion coefficients) of organic compounds reported by previous experimental studies, and we compare the measurement data to estimates obtained with Fuller's semi-empirical method. The difference between measured and estimated diffusivities are mostly < 10%. With regard to gas-particle interactions, different gas molecules, including both organic and inorganic compounds, exhibit similar Knudsen numbers (Kn) although their gas phase diffusivities may vary over a wide range. Knudsen numbers of gases with unknown diffusivity can be approximated by a simple function of particle diameter and pressure and can be used to characterize the influence of diffusion on gas uptake by aerosol or cloud particles. We use a kinetic multi-layer model of gas-particle interaction to illustrate the effects of gas phase diffusion on the condensation of organic compounds with different volatilities. The results show that gas-phase diffusion can play a major role in determining the growth of secondary organic aerosol particles by condensation of low-volatility organic vapours.

  4. Effect of duty-cycles on the air plasma gas-phase of dielectric barrier discharges

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    An experimental investigation concerning the effects of a duty-cycle in the supply of a dielectric barrier discharge in atmospheric pressure air has been performed. Electrical characteristics of the discharge have been measured, focusing mainly on the statistical properties of the current filaments and on dielectric surface charging, both affected by the frequent repetition of breakdown imposed by the duty-cycle. Information on the gas-phase composition was gathered too. In particular, a strong enhancement in the ozone formation rate is observed when suitable long pauses separate the active discharge phases. A simulation of the chemical kinetics in the gas-phase, based on a simplified discharge modeling, is briefly described in order to shed light on the observed increase in ozone production. The effect of a duty-cycle on surface modification of polymeric films in order to increase their wettability has been investigated too.

  5. Supramolecular reactivity in the gas phase: investigating the intrinsic properties of non-covalent complexes.

    PubMed

    Cera, Luca; Schalley, Christoph A

    2014-03-21

    The high vacuum inside a mass spectrometer offers unique conditions to broaden our view on the reactivity of supramolecules. Because dynamic exchange processes between complexes are efficiently suppressed, the intrinsic and intramolecular reactivity of the complexes of interest is observed. Besides this, the significantly higher strength of non-covalent interactions in the absence of competing solvent allows processes to occur that are unable to compete in solution. The present review highlights a series of examples illustrating different aspects of supramolecular gas-phase reactivity ranging from the dissociation and formation of covalent bonds in non-covalent complexes through the reactivity in the restricted inner phase of container molecules and step-by-step mechanistic studies of organocatalytic reaction cycles to cage contraction reactions, processes induced by electron capture, and finally dynamic molecular motion within non-covalent complexes as unravelled by hydrogen-deuterium exchange processes performed in the gas phase. PMID:24435245

  6. Computer code for gas-liquid two-phase vortex motions: GLVM

    NASA Technical Reports Server (NTRS)

    Yeh, T. T.

    1986-01-01

    A computer program aimed at the phase separation between gas and liquid at zero gravity, induced by vortex motion, is developed. It utilizes an explicit solution method for a set of equations describing rotating gas-liquid flows. The vortex motion is established by a tangential fluid injection. A Lax-Wendroff two-step (McCormack's) numerical scheme is used. The program can be used to study the fluid dynamical behavior of the rotational two-phase fluids in a cylindrical tank. It provides a quick/easy sensitivity test on various parameters and thus provides the guidance for the design and use of actual physical systems for handling two-phase fluids.

  7. FIELD METHODS TO MEASURE CONTAMINANT REMOVAL EFFECTIVENESS OF GAS-PHASE AIR FILTRATION EQUIPMENT - PHASE 1: SEARCH OF LITERATURE AND PRIOR ART

    EPA Science Inventory

    The report, Phase 1 of a two-phase research project, gives results of a literature search into the
    effectiveness of in-field gas-phase air filtration equipment (GPAFE) test methods, including required instrumentation and costs. GPAFE has been used in heating, ventilation, and ...

  8. Fluid Phase Separation (FPS) experiment for flight on a space shuttle Get Away Special (GAS) canister

    NASA Technical Reports Server (NTRS)

    Peters, Bruce; Wingo, Dennis; Bower, Mark; Amborski, Robert; Blount, Laura; Daniel, Alan; Hagood, Bob; Handley, James; Hediger, Donald; Jimmerson, Lisa

    1990-01-01

    The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid which will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on the Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS-42. The design and the production of a fluid phase separation experiment for rapid implementation at low cost is presented.

  9. A generalized expression for lag-time in the gas-phase permeation of hollow tubes

    NASA Technical Reports Server (NTRS)

    Shah, K. K.; Nelson, H. G.; Johnson, D. L.; Hamaker, F. M.

    1975-01-01

    A generalized expression for the nonsteady-state parameter, lag-time, has been obtained from Fick's second law for gas-phase transport through hollow, cylindrical membranes. This generalized expression is simplified for three limiting cases of practical interest: (1) diffusion controlled transport, (2) phase boundary reaction control at the inlet surface, and (3) phase boundary reaction control at the outlet surface. In all three cases the lag-time expressions were found to be inversely proportional only to the diffusion coefficient and functionally dependent on the membrane radii. Finally, the lag-time expressions were applied to experimentally obtained lag-time data for alpha-phase titanium and alpha-phase iron.

  10. Phase transition to Bose-Einstein condensation for a bosonic gas confined in a combined trap

    SciTech Connect

    Lue Baolong; Xiong Hongwei; Tan Xinzhou; Wang Bing; Cao Lijuan

    2010-11-15

    We present a study of phase transition to macroscopic superfluidity for an ultracold bosonic gas confined in a combined trap formed by a one-dimensional optical lattice and a harmonic potential, focusing on the critical temperature of this system and the interference patterns of the Bose gas released from the combined trap. Based on a semiclassical energy spectrum, we develop an analytic approximation for the critical temperature T{sub c}, and compare the analytic results with that obtained by numerical computations. For finite temperatures below T{sub c}, we calculate the interference patterns for both the normal gas and the superfluid gas. The total interference pattern shows a feature of 'peak on a peak'. As a comparison, we also present the experimentally observed interference patterns of {sup 87}Rb atoms released from a one-dimensional optical lattice system in accord with our theoretical model. Our observations are consistent with the theoretical results.

  11. LSPRAY: Lagrangian Spray Solver for Applications With Parallel Computing and Unstructured Gas-Phase Flow Solvers

    NASA Technical Reports Server (NTRS)

    Raju, Manthena S.

    1998-01-01

    Sprays occur in a wide variety of industrial and power applications and in the processing of materials. A liquid spray is a phase flow with a gas as the continuous phase and a liquid as the dispersed phase (in the form of droplets or ligaments). Interactions between the two phases, which are coupled through exchanges of mass, momentum, and energy, can occur in different ways at different times and locations involving various thermal, mass, and fluid dynamic factors. An understanding of the flow, combustion, and thermal properties of a rapidly vaporizing spray requires careful modeling of the rate-controlling processes associated with the spray's turbulent transport, mixing, chemical kinetics, evaporation, and spreading rates, as well as other phenomena. In an attempt to advance the state-of-the-art in multidimensional numerical methods, we at the NASA Lewis Research Center extended our previous work on sprays to unstructured grids and parallel computing. LSPRAY, which was developed by M.S. Raju of Nyma, Inc., is designed to be massively parallel and could easily be coupled with any existing gas-phase flow and/or Monte Carlo probability density function (PDF) solver. The LSPRAY solver accommodates the use of an unstructured mesh with mixed triangular, quadrilateral, and/or tetrahedral elements in the gas-phase solvers. It is used specifically for fuel sprays within gas turbine combustors, but it has many other uses. The spray model used in LSPRAY provided favorable results when applied to stratified-charge rotary combustion (Wankel) engines and several other confined and unconfined spray flames. The source code will be available with the National Combustion Code (NCC) as a complete package.

  12. Chemical models of interstellar gas-grain processes. II - The effect of grain-catalysed methane on gas phase evolution

    NASA Technical Reports Server (NTRS)

    Brown, Paul D.; Charnley, S. B.

    1991-01-01

    The effects on gas phase chemistry which result from the continuous desorption of methane molecules from grain surfaces are studied. Significant and sustained enhancements in the abundances of several complex hydrocarbon molecules are found, in good agreement with their observed values in TMC-1. The overall agreement is, however, just as good for the case of zero CH4 desorption efficiency. It is thus impossible to determine from the models whether or not the grain-surface production of methane is responsible for the observed abundances of some hydrocarbon molecules.

  13. Mechanism considerations for photocatalytic oxidation, ozonation and photocatalytic ozonation of some pharmaceutical compounds in water.

    PubMed

    Rodríguez, Eva M; Márquez, Gracia; León, Elena A; Álvarez, Pedro M; Amat, Ana M; Beltrán, Fernando J

    2013-09-30

    Aqueous solutions of four pharmaceutical compounds, belonging to the group of emergent contaminants of water: atenolol (ATL), hydrochlorothiazide (HCT), ofloxacin (OFX) and trimethoprim (TMP), have been treated with different oxidation systems, mainly, photocatalytic oxidation, ozonation and photocatalytic ozonation. TiO2 has been used as semiconductor for photocatalytic reactions both in the presence of air, oxygen or ozone-oxygen gas mixtures. Black light lamps mainly emitting at 365 nm were the source of radiation. In all cases, the influence of some variables (concentrations of semiconductor, ozone gas and pharmaceuticals and pH) on the removal of pharmaceuticals, total polyphenol content (TPC) and total organic carbon (TOC) was investigated. A discussion on the possible routes of pharmaceutical and intermediates (as TPC and TOC) elimination has been developed. Thus, OFX TiO2/UVA degradation mechanism seems to develop through the participation of non-hydroxyl free radical species. Furthermore, the presence of OFX inhibits the formation of hydroxyl radicals in the photocatalytic process. The most effective processes were those involving ozone that lead to complete disappearance of parent compounds in less than 30 min for initial pharmaceutical concentrations lower than 2.5 mg L(-1). In the ozonation systems, regardless of the pH and the presence of TiO2, pharmaceuticals are degraded through their direct reaction with ozone. Photocatalytic ozonation was the most efficient process for TPC and TOC removals (≥ 80% and ≥60% elimination after 2 h of treatment, respectively) as well as in terms of the ozone consumption efficiency (1, 5.5 and 4 mol of ozone consumed per mol of TOC mineralized, at pH 4, 7 and 9, respectively). Weakly acid conditions (pH 4) resulted to be the most convenient ones for TPC and TOC removal by photocatalytic ozonation. This was likely due to formation of hydroxyl radicals through the ozonide generated at these conditions. PMID

  14. The role of gas phase reactions in the deflagration-to-detonation transition of high energy propellants

    NASA Technical Reports Server (NTRS)

    Boggs, T. L.; Price, C. F.; Atwood, A. I.; Zurn, D. E.; Eisel, J. L.; Derr, R. L.

    1980-01-01

    The inadequacies of the two commonly used assumptions are shown, along with the need for considering gas phase reactions. Kinetic parameters that describe the gas phase reactions for several ingredients are provided, and the first steps in convective combustion leading to deflagration to detonation transition are described.

  15. The hydrothermal evolution of the phase and shape of ZnS nanostructures and their gas-sensing properties.

    PubMed

    Hu, Pengfei; Gong, Guodong; Zhan, Fangyi; Zhang, Yuan; Li, Rong; Cao, Yali

    2016-02-14

    This work presents the evolution of the phase and shape of ZnS along the hydrothermal holding time or the dosage of the surfactant. The ZnS sensor obviously showed phase-/defect-dependent gas-sensing performances indicating that the wurtzite-type structure, as well the defect will improve its gas-sensing activities. PMID:26781594

  16. Numerical Study of Gas-Phase Flow in a Cyclone Separator

    NASA Astrophysics Data System (ADS)

    Shi, Ya-Ping; Qu, Biao; Huang, Shan; Niu, Xiao-Dong

    2016-06-01

    To investigate separation efficiency of a cyclone separator at different operating parameters, in this paper we use Fluent software to numerically study the three dimensional gas-solid two-phase flows in the cyclone separator. The present work mainly consists four parts. Firstly we investigates the accuracy of different turbulent models including the standard k-ɛ model, RNG k-ɛ model, Realizable k-ɛ model and Reynolds stress equation model (RSM), and finds that the RSM turbulence model gives a good comparison between the numerical results and the experimental results. Secondly, the gas phase flow rate, pressure, and turbulent distribution in the cyclone separator are explored numerically in detail with the RSM model. Thirdly, on the base of the gas flow results, gas-solid two phase flows in the cyclone separator are studied by coupling the random trajectory model in the Lagrangian coordinates so that the particle trajectories in separator are displayed. Finally, effects of particle size and velocity at the cyclone separator inlet on the separation efficiency are analyzed. Numerical results show that when the particle velocity is higher and particle size is larger at the inlet, the separation efficiency is better. However, when the particle velocity and size approach their threshold values, the separation efficiency will not change.

  17. Design and Development of Gas-Liquid Cylindrical Cyclone Compact Separators for Three-Phase Flow

    SciTech Connect

    Mohan, Ram S.; Shoham, Ovadia

    1999-10-28

    The objective of this five-year project (October, 1997--September, 2002) is to expand the current research activities of Tulsa University Separation Technology Projects (TUSTP) to multiphase oil/water/gas separation. This project will be executed in two phases. Phase I (1997--2000) will focus on the investigations of the complex multiphase hydrodynamic flow behavior in a three-phase Gas-Liquid Cylindrical Cyclone (GLCC) Separator. The activities of this phase will include the development of a mechanistic model, a computational fluid dynamics (CFD) simulator, and detailed experimentation on the three-phase GLCC. The experimental and CFD simulation results will be suitably integrated with the mechanistic model. In Phase II (2000--2002), the developed GLCC separator will be tested under high pressure and real crudes conditions. This is crucial for validating the GLCC design for field application and facilitating easy and rapid technology deployment. Design criteria for industrial applications will be developed based on these results and will be incorporated into the mechanistic model by TUSTP.

  18. Design and Development of Gas-Liquid Cylindrical Cyclone Compact Separators for Three-Phase Flow

    SciTech Connect

    Mohan, R.S.; Shoham, O.

    2001-01-18

    The objective of this five-year project (October 1997 - September 2002) was to expand the current research activities of Tulsa University Separation Technology Projects (TUSTP) to multiphase oil/water/gas separation. This project was executed in two phases. Phase I (1997 - 2000) focused on the investigations of the complex multiphase hydrodynamic flow behavior in a three-phase Gas-Liquid Cylindrical Cyclone (GLCC) Separator. The activities of this phase included the development of a mechanistic model, a computational fluid dynamics (CFD) simulator, and detailed experimentation on the three-phase GLCC. The experimental and CFD simulation results will be suitably integrated with the mechanistic model. In Phase II (2000 - 2002), the developed GLCC separator will be tested under high pressure and real crude conditions. This is crucial for validating the GLCC design for field application and facilitating easy and rapid technology deployment. Design criteria for industrial applications will be developed based on these results and will be incorporated into the mechanistic model by TUSTP.

  19. Design and Development of Gas-Liquid Cylindrical Cyclone Compact Separators for Three-Phase Flow

    SciTech Connect

    Mohan, R.S.; Shoham, O.

    2001-01-10

    The objective of this five-year project (October 1997--September 2002) was to expand the current research activities of Tulsa University Separation Technology Projects (TUSTP) to multiphase oil/water/gas separation. This project was executed in two phases. Phase I (1997--2000) focused on the investigations of the complex multiphase hydrodynamic flow behavior in a three-phase Gas-Liquid Cylindrical Cyclone (GLCC) Separator. The activities of this phase included the development of a mechanistic model, a computational fluid dynamics (CFD) simulator, and detailed experimentation on the three-phase GLCC. The experimental and CFD simulation results will be suitably integrated with the mechanistic model. In Phase II (2000--2002), the developed GLCC separator will be tested under high pressure and real crude conditions. This is crucial for validating the GLCC design for field application and facilitating easy and rapid technology deployment. Design criteria for industrial applications will be developed based on these results and will be incorporated into the mechanistic model by TUSTP.

  20. DYNAMIC MODELING STRATEGY FOR FLOW REGIME TRANSITION IN GAS-LIQUID TWO-PHASE FLOWS

    SciTech Connect

    X. Wang; X. Sun; H. Zhao

    2011-09-01

    In modeling gas-liquid two-phase flows, the concept of flow regime has been used to characterize the global interfacial structure of the flows. Nearly all constitutive relations that provide closures to the interfacial transfers in two-phase flow models, such as the two-fluid model, are often flow regime dependent. Currently, the determination of the flow regimes is primarily based on flow regime maps or transition criteria, which are developed for steady-state, fully-developed flows and widely applied in nuclear reactor system safety analysis codes, such as RELAP5. As two-phase flows are observed to be dynamic in nature (fully-developed two-phase flows generally do not exist in real applications), it is of importance to model the flow regime transition dynamically for more accurate predictions of two-phase flows. The present work aims to develop a dynamic modeling strategy for determining flow regimes in gas-liquid two-phase flows through the introduction of interfacial area transport equations (IATEs) within the framework of a two-fluid model. The IATE is a transport equation that models the interfacial area concentration by considering the creation and destruction of the interfacial area, such as the fluid particle (bubble or liquid droplet) disintegration, boiling and evaporation; and fluid particle coalescence and condensation, respectively. For the flow regimes beyond bubbly flows, a two-group IATE has been proposed, in which bubbles are divided into two groups based on their size and shape (which are correlated), namely small bubbles and large bubbles. A preliminary approach to dynamically identifying the flow regimes is provided, in which discriminators are based on the predicted information, such as the void fraction and interfacial area concentration of small bubble and large bubble groups. This method is expected to be applied to computer codes to improve their predictive capabilities of gas-liquid two-phase flows, in particular for the applications in

  1. Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids from manufactured gas plants by reversed phase comprehensive two-dimensional gas chromatography.

    PubMed

    McGregor, Laura A; Gauchotte-Lindsay, Caroline; Daéid, Niamh Nic; Thomas, Russell; Daly, Paddy; Kalin, Robert M

    2011-07-22

    Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids (DNAPLs) from former manufactured gas plants (FMGPs) was investigated using comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GC×GC TOFMS). Reversed phase GC×GC (i.e. a polar primary column coupled to a non-polar secondary column) was found to significantly improve the separation of polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues. Sample extraction and cleanup was performed simultaneously using accelerated solvent extraction (ASE), with recovery rates between 76% and 97%, allowing fast, efficient extraction with minimal solvent consumption. Principal component analysis (PCA) of the GC×GC data was performed in an attempt to differentiate between twelve DNAPLs based on their chemical composition. Correlations were discovered between DNAPL composition and historic manufacturing processes used at different FMGP sites. Traditional chemical fingerprinting methods generally follow a tiered approach with sample analysis on several different instruments. We propose ultra resolution chemical fingerprinting as a fast, accurate and precise method of obtaining more chemical information than traditional tiered approaches while using only a single analytical technique. PMID:21652041

  2. Gas-Phase Lasers - a Historical Perspective in Relation to the GEC

    NASA Astrophysics Data System (ADS)

    Hays, Gerry

    1997-10-01

    Understanding of gas-phase lasers inevitably involves an expertise in many of the specialties of the GEC community - especially homogenous and heterogeneous kinetics, collision cross-sections, gas breakdown physics and fundamental swarm parameters. The GEC community decided early in the evolution of gas-phase lasers to include papers on this topic and the result was many years of contributions to the evolution of and improvement in our understanding of this important class of lasers. Many of the ground-breaking results in gas laser technology were presented at the GEC over the last 3 decades as the traditional rare-gas atomic physics and low-temperature plasma groups turned their attention to parameters of interest to the laser modelers and experimenters. This paper will trace the development of this field, especially as it pertained to the GEC. Some of the key results will be highlighted, together with some of the unpublished trivia and anecdotal incidents in order to capture the flavor of the rapid developments in the early days. The talk will include speculation as to the direction this field is taking, and some suggestions as to opportunities. This work supported by the United States Department of Energy under Contract DE-AC04-94AL85000. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the United States Department of Energy.

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

    SciTech Connect

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

    1991-01-01

    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{sub 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{sub 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 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 D, as will the other UF{sub 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{sub 6}. These reagents include ClF{sub 3}, F{sub 2}, and other compounds. The scope of D 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.

  4. Missing gas-phase source of HONO inferred from Zeppelin measurements in the troposphere

    NASA Astrophysics Data System (ADS)

    Li, Xin; Rohrer, Franz; Hofzumahaus, Andreas; Brauers, Theo; Häseler, Rolf; Bohn, Birger; Broch, Sebastian; Fuchs, Hendrik; Gomm, Sebastian; Holland, Frank; Jäger, Julia; Kaiser, Jennifer; Keutsch, Frank N.; Lohse, Insa; Tillmann, Ralf; Wegener, Robert; Wolfe, Glenn M.; Mentel, Thomas F.; Kiendler-Scharr, Astrid; Wahner, Andreas

    2014-05-01

    Nitrous acid (HONO) is an important trace gas in the atmosphere due to its contribution to the cycles of nitrogen oxides (NOX) and hydrogen oxides (HOX). In the past decades, ground-based observations of HONO around the world showed much higher daytime concentrations than can be explained by the known gas-phase chemistry (i.e., HONO + hν → OH + NO, HONO + OH → NO2 + H2O, OH + NO + M → HONO + M). Different light-dependent reactions on ground surfaces have been proposed as additional daytime HONO sources. However, due to lack of measurements, little is known about the concentrations of HONO and its sources in the planetary boundary layer (PBL) at higher altitudes above the earth's surface. The airship Zeppelin NT is an ideal platform to investigate the chemistry and dynamics of the PBL. During the PEGASOS field campaigns in 2012 and 2013, HONO and its gas-phase sources and sinks were measured simultaneously on-board the airship Zeppelin NT, for the lowest 1 km of the PBL. In the upper part of the altitude range during morning hours, when the airmass is still isolated from processes at the earth's surface by the remaining nocturnal boundary layer, we find unexpectedly large concentrations of HONO which can neither be explained by heterogeneous reactions on aerosol and ground surfaces, nor by known gas-phase reactions. Our observations show evidence for an unknown gas-phase light-dependent HONO production which dominates the overall HONO formation in the lower troposphere. This new HONO source requires NOX and possibly OH or HO2 radicals. As a result, the general impact of HONO on the OH formation is likely overestimated.

  5. The use of gas-phase substrates to study enzyme catalysis at low hydration.

    PubMed Central

    Dunn, Rachel V; Daniel, Roy M

    2004-01-01

    Although there are varying estimates as to the degree of enzyme hydration required for activity, a threshold value of ca. 0.2 g of water per gram of protein has been widely accepted. The evidence upon which this is based is reviewed here. In particular, results from the use of gas-phase substrates are discussed. Results using solid-phase enzyme-substrate mixtures are not altogether in accord with those obtained using gas-phase substrates. The use of gaseous substrates and products provides an experimental system in which the hydration of the enzyme can be easily controlled, but which is not limited by diffusion. All the results show that increasing hydration enhances activity. The results using gas-phase substrates do not support the existence of a critical hydration value below which enzymatic activity is absent, and suggest that enzyme activity is possible at much lower hydrations than previously thought; they do not support the notion that significant hydration of the surface polar groups is required for activity. However, the marked improvement of activity as hydration is increased suggests that water does play a role, perhaps in optimizing the structure or facilitating the flexibility required for maximal activity. PMID:15306385

  6. Carbonyl Compounds in the Gas Phase of Cigarette Mainstream Smoke and Their Pharmacological Properties.

    PubMed

    Horinouchi, Takahiro; Higashi, Tsunehito; Mazaki, Yuichi; Miwa, Soichi

    2016-01-01

    Cigarette mainstream smoke is composed of gas and tar phases and contains >4000 chemical constituents, including nicotine and tar. The substances in the gas phase but not in the tar phase can pass through the airway epithelial barrier, enter the systemic circulation via the pulmonary circulation, and increase systemic oxidative damage, leading to the development of cigarette smoking-related diseases such as atherosclerosis. Recently, we identified some stable carbonyl compounds, including acrolein (ACR) and methyl vinyl ketone (MVK), as major cytotoxic factors in nicotine- and tar-free cigarette smoke extract (CSE) of the gas phase. CSE, ACR, and MVK induce protein kinase C (PKC)-dependent activation of reduced nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (NOX) and subsequent generation of reactive oxygen species (ROS) via NOX, causing plasma membrane damage and cell apoptosis. CSE, ACR, and MVK also trigger carbonylation of PKC, which is an irreversible oxidative modification. Cell damage and PKC carbonylation in response to treatment with CSE, ACR, or MVK are abolished by thiol-containing antioxidants such as N-acetyl-L-cysteine and reduced glutathione. Thus pharmacological modulation of PKC and NOX activities and the trapping of ROS are potential strategies for the prevention of diseases related to cigarette smoking. PMID:27251492

  7. Temperature dependence of the particle/gas partition coefficient: An application to predict indoor gas-phase concentrations of semi-volatile organic compounds.

    PubMed

    Wei, Wenjuan; Mandin, Corinne; Blanchard, Olivier; Mercier, Fabien; Pelletier, Maud; Le Bot, Barbara; Glorennec, Philippe; Ramalho, Olivier

    2016-09-01

    The indoor gas-phase concentrations of semi-volatile organic compounds (SVOCs) can be predicted from their respective concentrations in airborne particles by applying the particle/gas partitioning equilibrium. The temperature used for partitioning is often set to 25°C. However, indoor temperatures frequently differ from this reference value. This assumption may result in errors in the predicted equilibrium gas-phase SVOC concentrations. To improve the prediction model, the temperature dependence of the particle/gas partition coefficient must be addressed. In this paper, a theoretical relationship between the particle/gas partition coefficient and temperature was developed based on the SVOC absorptive mechanism. The SVOC particle/gas partition coefficients predicted by employing the derived theoretical relationship agree well with the experimental data retrieved from the literature (R>0.93). The influence of temperature on the equilibrium gas-phase SVOC concentration was quantified by a dimensionless analysis of the derived relationship between the SVOC particle/gas partition coefficient and temperature. The predicted equilibrium gas-phase SVOC concentration decreased by between 31% and 53% when the temperature was lowered by 6°C, while it increased by up to 750% when the indoor temperature increased from 15°C to 30°C. PMID:27152992

  8. Ratio of solid to gas phase CO in the line of sight to W33A

    SciTech Connect

    Mitchell, G.F.; Allen, M.; Maillard, J.P.

    1988-10-01

    Spectroscopic observations of the IR source W33A, obtained in the M band (4.6 microns) at resolution 0.057/cm using the Fourier-transform spectrometer at the Cassegrain focus of the Canada-France-Hawaii Telescope on July 12-13, 1987, are reported. The spectrum is shown, and equivalent widths and CO column densities are presented in tables. The absorption lines detected indicate the presence of gas at both 23 and 120 K, attributed to the molecular-cloud core and gas near the source, respectively, but very little solid-phase CO. 11 references.

  9. Risk Assessment Related to Atmospheric Polycyclic Aromatic Hydrocarbons in Gas and Particle Phases near Industrial Sites

    PubMed Central

    Ramírez, Noelia; Cuadras, Anna; Marcé, Rosa Maria

    2011-01-01

    Background: Inhalation is one of the main means of human exposure to polycyclic aromatic hydrocarbons (PAHs) because of their ubiquitous presence in the atmosphere. However, most studies have considered only PAHs found in the particle phase and have omitted the contribution of the gas-phase PAHs to the risk. Objective: We estimated the lifetime lung cancer risk from PAH exposure by inhalation in people living next to the largest chemical site in Southern Europe and the Mediterranean area. Methods: We determined 18 PAHs in the atmospheric gas and particle phase. We monitored the PAHs for 1 year in three locations near the chemical site in different seasons. We used toxic equivalence factors to calculate benzo[a]pyrene (BaP) equivalents (BaP-eq) for individual PAHs and applied the World Health Organization unit risk (UR) for BaP (UR = 8.7 × 10–5) to estimate lifetime cancer risks due to PAH exposures. Results: We observed some spatial and seasonal variability in PAH concentrations. The contribution of gas-phase PAHs to the total BaP-eq value was between 34% and 86%. The total estimated average lifetime lung cancer risk due to PAH exposure in the study area was 1.2 × 10–4. Conclusions: The estimated risk was higher than values recommended by the World Health Organization and U.S. Environmental Protection Agency but lower than the threshold value of 10–3 that is considered an indication of definite risk according to similar risk studies. The results also showed that risk may be underestimated if the contributions of gas-phase PAHs are not considered. PMID:21478082

  10. Terpenes in the gas phase: The structural conformation of S-(-)-perillaldehyde investigated by microwave spectroscopy and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Avilés Moreno, Juan Ramón; Partal Ureña, Francisco; López González, Juan Jesús; Huet, Thérèse R.

    2009-04-01

    S-(-)-perillaldehyde (C 10H 14O) has been characterized in the gas phase using a Fourier transform microwave spectroscopy experiment in a supersonic molecular beam. Two conformers - with the isopropenyl group in the equatorial position - have been detected and described by a set of molecular parameters including the principal rotational constants and the quartic centrifugal distortion parameters. Quantum chemical calculations indicate that a third conformer might not be observed due to relaxation processes in the jet. The gas phase results are compared with the liquid phase IR-Raman-VCD spectra. Our study shows that gas phase spectroscopy is a powerful tool for characterizing monoterpenes.

  11. Gas-phase chemistry in dense interstellar clouds including grain surface molecular depletion and desorption

    NASA Technical Reports Server (NTRS)

    Bergin, E. A.; Langer, W. D.; Goldsmith, P. F.

    1995-01-01

    We present time-dependent models of the chemical evolution of molecular clouds which include depletion of atoms and molecules onto grain surfaces and desorption, as well as gas-phase interactions. We have included three mechanisms to remove species from the grain mantles: thermal evaporation, cosmic-ray-induced heating, and photodesorption. A wide range of parameter space has been explored to examine the abundance of species present both on the grain mantles and in the gas phase as a function of both position in the cloud (visual extinction) and of evolutionary state (time). The dominant mechanism that removes molecules from the grain mantles is cosmic-ray desorption. At times greater than the depletion timescale, the abundances of some simple species agree with abundances observed in the cold dark cloud TMC-1. Even though cosmic-ray desorption preserves the gas-phase chemistry at late times, molecules do show significant depletions from the gas phase. Examination of the dependence of depletion as a function of density shows that when the density increases from 10(exp 3)/cc to 10(exp 5)/cc several species including HCO(+), HCN, and CN show gas-phase abundance reductions of over an order of magnitude. The CO: H2O ratio in the grain mantles for our standard model is on the order of 10:1, in reasonable agreement with observations of nonpolar CO ice features in rho Ophiuchus and Serpens. We have also examined the interdependence of CO depletion with the space density of molecular hydrogen and binding energy to the grain surface. We find that the observed depletion of CO in Taurus in inconsistent with CO bonding in an H2O rich mantle, in agreement with observations. We suggest that if interstellar grains consist of an outer layer of CO ice, then the binding energies for many species to the grain mantle may be lower than commonly used, and a significant portion of molecular material may be maintained in the gas phase.

  12. Absorbance characteristics of a liquid-phase gas sensor based on gas-permeable liquid core waveguides.

    PubMed

    Peng, Pei; Wang, Wei; Zhang, Li; Su, Shiguang; Wang, Jiahui

    2013-12-01

    The absorbance characteristics and influential factors on these characteristics for a liquid-phase gas sensor, which is based on gas-permeable liquid core waveguides (LCWs), are studied from theoretical and experimental viewpoints in this paper. According to theory, it is predicted that absorbance is proportional to the analyte concentration, sampling time, analyte diffusion coefficient, and geometric factor of this device when the depletion layer of the analyte is ignored. The experimental results are in agreement with the theoretical hypothesis. According to the experimental results, absorbance is time-dependent and increasing linearly over time after the requisite response time with a linear correlation coefficient r(2)>0.999. In the linear region, the rate of absorbance change (RAC) indicates improved linearity with sample concentration and a relative higher sensitivity than instantaneous absorbance does. By using a core liquid that is more affinitive to the analyte, reducing wall thickness and the inner diameter of the tubing, or increasing sample flow rate limitedly, the response time can be decreased and the sensitivity can be increased. However, increasing the LCW length can only enhance sensitivity and has no effect on response time. For liquid phase detection, there is a maximum flow rate, and the absorbance will decrease beyond the stated limit. Under experimental conditions, hexane as the LCW core solvent, a tubing wall thickness of 0.1 mm, a length of 10 cm, and a flow rate of 12 mL min(-1), the detection results for the aqueous benzene sample demonstrate a response time of 4 min. Additionally, the standard curve for the RAC versus concentration is RAC=0.0267c+0.0351 (AU min(-1)), with r(2)=0.9922 within concentrations of 0.5-3.0 mg L(-1). The relative error for 0.5 mg L(-1) benzene (n=6) is 7.4±3.7%, and the LOD is 0.04 mg L(-1). This research can provide theoretical and practical guides for liquid-phase gas sensor design and development based on a

  13. Phase Separation, Density Fluctuations, and Boiling Near the Liquid-Gas Critical Point

    NASA Astrophysics Data System (ADS)

    Hegseth, John; Oprisan, Ana; Roy, Arun; Nikolayev, Vadim; Beysens, Daniel; Garrabos, Yves; Lecoutre-Chabot, Carole

    2002-11-01

    A pure liquid-gas mixture is one of the simplest examples of a soft-matter system. In fact, when co-existing gas and liquid phases of pure fluid are heated to their critical point, large-scale density fluctuations make the fluid extremely compressible (to external forces), expandable (to heating), slows the diffusive transport, and decreases the surface tension. In principle these properties and others either diverge to infinity or converge to zero at the critical temperature. These properties lead to some very unusual behavior: large density gradients at the laboratory scale, a large mechanical response to heating, and perfect wetting of a solid wall by the liquid phase (zero contact-angle). We have further simplified this system by performing experiments in weightlessness (Mir spaces station). By controlling the fluid's temperature, these properties may be varied over large ranges in a single sample. When the fluid is driven out of equilibrium by a fast temperature quench from the single-phase (supercritical fluid) state into the two-phase state, we have observed universal growth laws of minority domains (gas bubbles) during phase separation. Prior to this quench we have also observed density fluctuations using optical microscopy near the critical point. When heat is applied to a liquid-gas mixture, we have observed a spectacular spreading of a gas bubble along a hot solid wall as well as gas bubble over-heating (where the interior of a gas bubble gains a higher temperature than the heating wall). Although this gas phase over-heating appears to violate the second law, it is really a transient our-of-equilibrium effect. Inside of these unusual bubbles we also have observed unusually large variations in liquid wetting film thickness that often appear to evolve into spreading contact lines on the sapphire wall when heat is applied. We have observed coarsening and growth of minority domains (gas bubbles) in SF6 near its liquid-gas critical point. Phase separation in

  14. Chromatographic sample collection from two-phase (gas+liquid) flows.

    PubMed

    Bruno, Thomas J; Windom, Bret C

    2011-12-01

    A particularly challenging sample presentation in analytical chemistry is a flowing stream that consists of both a gas and liquid phase, combined with the common situation in which a reliable analysis is needed for both phases, separately. In these cases, the vapor and liquid must be physically separated (without change to either), before the individual phases can be collected and analyzed. It is not possible to analyze two-phase flows otherwise. Although the two phases are at equilibrium, it is imperative that no liquid contaminate the vapor, and no vapor be entrained in the liquid at a given temperature and pressure. In this paper, we describe a simple on-line device that can individually separate and collect the vapor and liquid phases of a two-phase flow. The apparatus, which we call P(2)SC, uses an adaptation of the branch point separator, with vapor collection done downstream in a metal bellows. The liquid collection is done in a length of Teflon tube. The separated vapor and liquid phases are then easily transferred into any desired analytical instrument with a syringe, although any sample introduction method, such as a valve, could be used as well. We discuss the application of this device with a stream of thermally stressed rocket kerosene. PMID:22036084

  15. A Chain of Modeling Tools For Gas and Aqueous Phase Chemstry

    NASA Astrophysics Data System (ADS)

    Audiffren, N.; Djouad, R.; Sportisse, B.

    Atmospheric chemistry is characterized by the use of large set of chemical species and reactions. Handling with the set of data required for the definition of the model is a quite difficult task. We prsent in this short article a preprocessor for diphasic models (gas phase and aqueous phase in cloud droplets) named SPACK. The main interest of SPACK is the automatic generation of lumped species related to fast equilibria. We also developped a linear tangent model using the automatic differentiation tool named ODYSSEE in order to perform a sensitivity analysis of an atmospheric multi- phase mechanism based on RADM2 kinetic scheme.Local sensitivity coefficients are computed for two different scenarii. We focus in this study on the sensitivity of the ozone,NOx,HOx, system with respect to some aqueous phase reactions and we inves- tigate the influence of the reduction in the photolysis rates in the area below the cloud region.

  16. Source reconciliation of atmospheric gas-phase and particle-phase pollutants during a severe photochemical smog episode.

    PubMed

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

    2002-09-01

    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

  17. CFD simulation of gas and non-Newtonian fluid two-phase flow in anaerobic digesters.

    PubMed

    Wu, Binxin

    2010-07-01

    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. PMID:20627353

  18. Single-shot gas-phase thermometry by time-to-frequency mapping of coherence dephasing.

    PubMed

    Yue, Orin; Bremer, Marshall T; Pestov, Dmitry; Gord, James R; Roy, Sukesh; Dantus, Marcos

    2012-08-01

    We demonstrate a single-beam coherent anti-Stokes Raman scattering (CARS) technique for gas-phase thermometry that assesses the species-specific local gas temperature by single-shot time-to-frequency mapping of Raman-coherence dephasing. The proof-of-principle experiments are performed with air in a temperature-controlled gas cell. Impulsive excitation of molecular vibrations by an ultrashort pump/Stokes pulse is followed by multipulse probing of the 2330 cm(-1) Raman transition of N(2). This sequence of colored probe pulses, delayed in time with respect to each other and corresponding to three isolated spectral bands, imprints the coherence dephasing onto the measured CARS spectrum. For calibration purposes, the dephasing rates are recorded at various gas temperatures, and the relationship is fitted to a linear regression. The calibration data are then used to determine the gas temperature and are shown to provide better than 15 K accuracy. The described approach is insensitive to pulse energy fluctuations and can, in principle, gauge the temperature of multiple chemical species in a single laser shot, which is deemed particularly valuable for temperature profiling of reacting flows in gas-turbine combustors. PMID:22747235

  19. Site-selective patterning of organic luminescent molecules via gas phase deposition.

    PubMed

    Hao, Juanyuan; Lu, Nan; Wu, Qiong; Hu, Wei; Chen, Xiaodong; Zhang, Hongyu; Wu, Ying; Wang, Yue; Chi, Lifeng

    2008-05-20

    In this paper, we present a bottom-up approach to pattern organic luminescent molecules with a feature size down to sub-100 nm over wafer-sized areas. This method is based on the selective gas deposition of organic molecules on self-organized patterned structures, which consist of an organic monolayer with two different phases rather than different materials. The site selectivity is controllable by deposition rate and the pattern features. The reason for the site selectivity may be due to the nucleation and diffusion behaviors of the deposited organic molecules on different monolayer phases. PMID:18370416

  20. Gas-Phase Molecular Dynamics: Theoretical Studies In Spectroscopy and Chemical Dynamics

    SciTech Connect

    Yu H. G.; Muckerman, J.T.

    2012-05-29

    The main goal of this program is the development and application of computational methods for studying chemical reaction dynamics and molecular spectroscopy in the gas phase. We are interested in developing rigorous quantum dynamics algorithms for small polyatomic systems and in implementing approximate approaches for complex ones. Particular focus is on the dynamics and kinetics of chemical reactions and on the rovibrational spectra of species involved in combustion processes. This research also explores the potential energy surfaces of these systems of interest using state-of-the-art quantum chemistry methods, and extends them to understand some important properties of materials in condensed phases and interstellar medium as well as in combustion environments.

  1. Fluorometric method for the determination of gas-phase hydrogen peroxide

    NASA Technical Reports Server (NTRS)

    Kok, Gregory L.; Lazrus, Allan L.

    1986-01-01

    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.

  2. Finite-momentum superfluidity and phase transitions in a p-wave resonant Bose gas

    SciTech Connect

    Choi, Sungsoo; Radzihovsky, Leo

    2011-10-15

    We study a degenerate two-species gas of bosonic atoms interacting through a p-wave Feshbach resonance as, for example, realized in a {sup 85}Rb-{sup 87}Rb mixture. We show that, in addition to a conventional atomic and a p-wave molecular spinor-1 superfluidity at large positive and negative detunings, respectively, the system generically exhibits a finite-momentum atomic-molecular superfluidity at intermediate detuning around the unitary point. We analyze the detailed nature of the corresponding phases and the associated quantum and thermal phase transitions.

  3. Nanocomposite exchange-spring magnet synthesized by gas phase method: From isotropic to anisotropic

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoqi; He, Shihai; Qiu, Jiao-Ming; Wang, Jian-Ping

    2011-05-01

    The fabrication of anisotropic nanocomposite exchange-spring magnets is demonstrated experimentally by using a gas-phase nanoparticle deposition technique. High resolution transmission electron microscopy images prove the experimental easy-axis definition of embedded hard magnetic nanoparticles in soft magnetic matrix. Exchange coupling between the hard and soft phases is confirmed by measuring recoil loops and δ M-H curve of the anisotropic FePt/Fe0.8Ni0.2 nanocomposite. The magnetic energy product for the anisotropic exchange-spring magnet is 224% higher than the isotropic case.

  4. Biologically Inspired Photocatalytically Active Membranes for Water Treatment

    NASA Astrophysics Data System (ADS)

    Kinsinger, Nichola M.

    There is an alarming increase of a variety of new chemicals that are now being discharged into the wastewater system causing increased concern for public health and safety because many are not removed by typical wastewater treatment practices. Titanium Dioxide (TiO2) is a heterogeneous photocatalytic material that rapidly and completely mineralizing organics without harmful byproducts. TiO2 is synthesized by various methods, which lack the necessary control of crystal size, phase, and morphological features that yield optimized semiconductor materials. Mineralizing organisms demonstrate how nature can produce elegant structures at room temperature through controlled organic-mineral interactions. Here, we utilize biologically-inspired scaffolds to template the nucleation and growth of inorganic materials such as TiO2, which aid in controlling the size and phase of these particles and ultimately, their properties. Nanosized rutile and anatase particles were synthesized under solution conditions at relatively low temperatures and mild pH conditions. The effects of reaction conditions on phase and grain size were investigated and discussed from coordination chemistry and coarsening mechanisms. Photocatalytic characterization of TiO2 phase mixtures was performed to investigate their synergistic effect. The suspension conditions of these catalytic nanomaterials were modulated to optimize the degradation rate of organic analytes. Through the addition of an organic scaffold during the synthesis reaction, a mechanically robust (elastic) composite material containing TiO2 nanoparticles was produced. This composite was subsequently heat-treated to produce a porous, high surface area TiO2 nanoparticulate membrane. Processing conditions were investigated to characterize the growth and phase transformation of TiO2, which ultimately impacts photocatalytic performance. These bulk porous TiO2 structures can be fabricated and tailored to act as stand-alone photocatalytic membranes

  5. Gas phase versus surface contributions to photolytic laser chemical vapor deposition rates

    NASA Astrophysics Data System (ADS)

    Braichotte, D.; van den Bergh, H.

    1988-04-01

    The rate of cw photolytic laser chemical vapor deposition (LCVD) of platinum is measured for λ≈350 nm as a function of the light intensity and the metalorganic vapor pressure. The growth of the metal films is studied in situ and in real time by monitoring their optical transmission. At low intensities the transmitted light decreases monotonically with time, and the LCVD process is photolytic with its rate limiting step in the surface adlayer. At higher intensities we observe two distinct time domains: Relatively slow initial photolytic deposition with its rate limiting step in the gas phase, which is followed by much faster pyrolytic LCVD. An improved method for distinguishing between adlayer and gas-phase limiting processes is demonstrated. These observations are confirmed by studying the photolytic deposition rates while varying the thickness of the adlayer.

  6. Methods and apparatus for using gas and liquid phase cathodic depolarizers

    NASA Technical Reports Server (NTRS)

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

    1998-01-01

    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.

  7. Decay of the 3D inviscid liquid-gas two-phase flow model

    NASA Astrophysics Data System (ADS)

    Zhang, Yinghui

    2016-06-01

    We establish the optimal {Lp-L2(1 ≤ p < 6/5)} time decay rates of the solution to the Cauchy problem for the 3D inviscid liquid-gas two-phase flow model and analyze the influences of the damping on the qualitative behaviors of solution. Compared with the viscous liquid-gas two-phase flow model (Zhang and Zhu in J Differ Equ 258:2315-2338, 2015), our results imply that the friction effect of the damping is stronger than the dissipation effect of the viscosities and enhances the decay rate of the velocity. Our proof is based on Hodge decomposition technique, the {Lp-L2} estimates for the linearized equations and an elaborate energy method.

  8. Activation of gas-phase uranyl: from an oxo to a nitrido complex.

    PubMed

    Gong, Yu; Vallet, Valérie; Michelini, Maria del Carmen; Rios, Daniel; Gibson, John K

    2014-01-01

    The uranyl moiety, UO2(2+), is ubiquitous in the chemistry of uranium, the most prevalent actinide. Replacing the strong uranium-oxygen bonds in uranyl with other ligands is very challenging, having met with only limited success. We report here uranyl oxo bond activation in the gas phase to form a terminal nitrido complex, a previously elusive transformation. Collision induced dissociation of gas-phase UO2(NCO)Cl2(-) in an ion trap produced the nitrido oxo complex, NUOCl2(-), and CO2. NUOCl2(-) was computed by DFT to have Cs symmetry and a singlet ground state. The computed bond length and order indicate a triple U-N bond. Endothermic activation of UO2(NCO)Cl2(-) to produce NUOCl2(-) and neutral CO2 was computed to be thermodynamically more favorable than NCO ligand loss. Complete reaction pathways for the CO2 elimination process were computed at the DFT level. PMID:24354492

  9. Properties of clusters in the gas phase. V - Complexes of neutral molecules onto negative ions

    NASA Technical Reports Server (NTRS)

    Keesee, R. G.; Lee, N.; Castleman, A. W., Jr.

    1980-01-01

    Ion-molecules association reactions of the form A(-)(B)n-1 + B = A(-)(B)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 NO2(-) with n ranging from one to three or four, and onto SO2(-) and SO3(-) with n equal to one; and (2) carbon dioxide onto Cl(-), I(-), NO2(-), CO3(-), and SO3(-) 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.

  10. Unusual hydroxyl migration in the fragmentation of β-alanine dication in the gas phase.

    PubMed

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

    2015-07-14

    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. PMID:26035826

  11. Elusive Sulfurous Acid: Gas-Phase Basicity and IR Signature of the Protonated Species.

    PubMed

    Sinha, Rajeev K; Scuderi, Debora; Maitre, Philippe; Chiavarino, Barbara; Crestoni, Maria Elisa; Fornarini, Simonetta

    2015-05-01

    The ion corresponding to protonated sulfurous acid, H3SO3(+), has been successfully delivered into the gas phase by electrospray ionization of the solution of a suitable precursor and an in-source fragmentation process. The neutral acid is a highly elusive molecule. However, its gas-phase basicity has been ascertained by means of a kinetic study of proton-transfer reactivity. The structure of the H3SO3(+) sampled ion has been probed by IRMPD spectroscopy in two complementary IR frequency ranges in conjunction with density functional theory calculations and found to conform to a trihydroxosulfonium ion. The characteristic IR signatures may aid in deciphering the presence of this species in extraterrestrial atmospheres. PMID:26263321

  12. Anchoring the gas-phase acidity scale: From formic acid to methanethiol

    NASA Astrophysics Data System (ADS)

    Eyet, Nicole; Villano, Stephanie M.; Bierbaum, Veronica M.

    2009-06-01

    We have measured the gas-phase acidities of nine compounds: formic acid, acetic acid, 1,3-propanedithiol, 2-methyl-2-propanethiol, 3-methyl-1-butanethiol, 2-propanethiol, 1-propanethiol, ethanethiol, and methanethiol, with acidities ranging from 338.6 to 351.1 kcal mol-1 using proton transfer kinetics and the resulting equilibrium constants. These acids were anchored to the well-known acidity of hydrogen sulfide; the measured acidities are in good agreement with previous experimental values, but error bars are significantly reduced. The gas-phase acidity of 3-methyl-1-butanethiol was determined to be 347.1 (5) kcal mol-1; there were no previous measurements of this value. Entropies of deprotonation were calculated and enthalpies of deprotonation were determined.

  13. Gas-phase acidities of tetrahedral oxyacids from ab initio electronic structure theory

    SciTech Connect

    Rustad, J.R.; Dixon, D.A.; Kubicki, J.D.; Felmy, A.R.

    2000-05-04

    Density functional calculations have been performed on several protonation states of the oxyacids of Si, P, V, As, Cr, and S. Structures and vibrational frequencies are in good agreement with experimental values where these are available. A reasonably well-defined correlation between the calculated gas-phase acidities and the measured pK{sub a} in aqueous solution has been found. The pK{sub a}/gas-phase acidity slopes are consistent with those derived from previous molecular mechanics calculations on ferric hydrolysis and the first two acidity constants for orthosilicic acid. The successive deprotonation of other H{sub n}TO{sub 4} species, for a given tetrahedral anion T are roughly consistent with this slope, but not to the extent that there is a universal correlation among all species.

  14. Transport simulations of the pre-thermal-quench phase in ASDEX Upgrade massive gas injection experiments

    NASA Astrophysics Data System (ADS)

    Fable, E.; Pautasso, G.; Lehnen, M.; Dux, R.; Bernert, M.; Mlynek, A.; the ASDEX Upgrade Team

    2016-02-01

    The pre-thermal-quench (PTQ) phase of the massive gas injection (MGI) scenario to terminate the tokamak plasma discharge is studied by means of one-dimensional (1D) transport simulations. This phase is characterized by the cold-front penetration in the hot plasma after the gas has been released from the valves, and before the actual thermal quench takes place, with consequent plasma disruption at lower stored energy. The comparison between the simulations and the ASDEX Upgrade (AUG) experiments allows to gain insight in the observed dependencies and time scales. Despite the genuine three-dimensional structure of the problem, it is shown that the 1D simulations are already giving experimentally relevant answers, the reason for which will be discussed in detail. Influence of unknown parameters and simplifying assumptions are also discussed.

  15. Formation of organic acids from the gas-phase ozonolysis of terpinolene.

    PubMed

    Ma, Yan; Marston, George

    2009-06-01

    Gas-phase ozonolysis of terpinolene was studied in static chamber experiments using gas chromatography coupled to mass spectrometric and flame ionisation detection to separate and detect products. Two isomers of C(7)-diacids and three isomers of C(7)-aldehydic acids were identified in the condensed phase after derivatisation. Possible mechanisms of formation of these acids were investigated using different OH radical scavengers and relative humidities, and were compared to those reported earlier for the ozonolysis of beta-pinene. In addition, branching ratios for some of the individual reaction steps, e.g. the branching ratio between the two hydroperoxide channels of the C(7)-CI, were deduced from the quantitative product yield data. Branching ratios for POZ decomposition and the stabilisation/decomposition of the C(7-)CI were also obtained from measurements of the C(7) primary carbonyl product. PMID:19458821

  16. Fundamental studies of gas phase ionic reactions by ion mobility spectrometry

    NASA Technical Reports Server (NTRS)

    Giles, K.; Knighton, W. B.; Sahlstrom, K. E.; Grimsrud, E. P.

    1995-01-01

    Ion mobility spectrometry (IMS) provides a promising approach to the study of gas phase ionic reactions in buffer gases at unusually high pressures. This point is illustrated here by studies of the Sn2 nucleophilic displacement reaction, Cl(-) + CH3Br yields Br + CH3Br, using IMS at atmospheric pressure. The equilibrium clustering reaction, Cl(-)(CHCI3)(n - 1) + CHCI3 yields Cl(-)(CHCI3)(n), where n = 1 and 2, and the effect of clustering on the Sn2 reaction with CH3Br have also been characterized by this IMS-based kinetic method. Present problems and anticipated improvements in the application of ion mobility spectrometry to studies of other gas phase ionic processes are discussed.

  17. Polar Effects Control the Gas-phase Reactivity of Charged para-Benzyne Analogs

    PubMed Central

    Wittrig, Ashley M.; Archibold, Enada F.; Sheng, Huaming; Nash, John J.; Kenttämaa, Hilkka I.

    2014-01-01

    The gas-phase reactivity of charged para-benzynes is entirely unexplored as they and/or their precursors tend to undergo ring-opening upon their generation. We report here a gas-phase reactivity study of two such benzynes, the 2,5-didehydropyridinium and 5,8-didehydroisoquinolinium cations, generated in a modified dual-linear quadrupole ion trap (DLQIT) mass spectrometer. Both biradicals were found to form diagnostic products with organic molecules, indicating the presence of two radical sites. As opposed to earlier predictions that the singlet-triplet (S-T) splitting controls the radical reactivity of such species, the 2,5-didehydropyridinium cation reacts much faster in spite of its larger S-T splitting. Calculated vertical electron affinities of the radical sites of the para-benzynes, a parameter related to the polarity of the transition states of their reactions, appears to be the most important reactivity controlling factor. PMID:25838787

  18. Kinetics and mechanisms of UV-photodegradation of chlorinated organics in the gas phase.

    PubMed

    Feiyan, Chen; Pehkonen, S O; Ray, Madhumita B

    2002-10-01

    Over the last two decades, the application of photodegradation for the destruction of a wide spectrum of organic compounds in air has gained considerable interest in abating environmental pollution. This paper presents the results of a fundamental study conducted to evaluate the gas phase oxidation kinetics of volatile organic compounds (VOCs) with respect to different parameters pertinent to the operating conditions of air stripping and soil vapor extraction processes. Photodegradations of three chlorinated VOCs: chloroform, carbon tetrachloride (CTC) and trichloroethylene (TCE), were investigated in a semi-batch reactor using a low-pressure mercury UV lamp. The effects of different experimental parameters, such as the initial concentrations of the VOCs, the reaction medium, relative humidity, light intensity, temperature and the effect of mixture that may influence the kinetics of the gas phase photodegradation were evaluated. Mechanisms of photodegradation as supported by the experimental data are also proposed. PMID:12420925

  19. Gas-Phase Femtosecond Particle Spectroscopy: A Bottom-Up Approach to Nucleotide Dynamics.

    PubMed

    Stavros, Vasilios G; Verlet, Jan R R

    2016-05-27

    We summarize how gas-phase ultrafast charged-particle spectroscopy has been used to provide an understanding of the photophysics of DNA building blocks. We focus on adenine and discuss how, following UV excitation, specific interactions determine the fates of its excited states. The dynamics can be probed using a systematic bottom-up approach that provides control over these interactions and that allows ever-larger complexes to be studied. Starting from a chromophore in adenine, the excited state decay mechanisms of adenine and chemically substituted or clustered adenine are considered and then extended to adenosine mono-, di-, and trinucleotides. We show that the gas-phase approach can offer exquisite insight into the dynamics observed in aqueous solution, but we also highlight stark differences. An outlook is provided that discusses some of the most promising developments in this bottom-up approach. PMID:26980306

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  1. Simulation of a turbulent spray flame using coupled PDF gas phase and spray flamelet modeling

    SciTech Connect

    Ge, Hai-Wen; Gutheil, Eva

    2008-04-15

    A joint mixture fraction-enthalpy probability density function (PDF) is proposed for the simulation of turbulent spray flames. The PDF transport equation is deduced and modeled. The interaction-by-exchange-with-the-mean (IEM) model that has been developed for gas-phase flows is extended to describe molecular mixing in nonreactive and reactive spray flows. The joint PDF transport equation is solved by a hybrid finite-volume and Lagrangian Monte Carlo method. Standard spray and turbulence models are used to describe the gas phase and the liquid phase. A turbulent methanol/air spray flame is simulated using the present method. Detailed chemistry is implemented through the spray flamelet model. The precalculated spray flamelet library for methanol/air combustion comprises 23 species and 168 elementary reactions. Thus, the model is capable of predicting the formation of radicals and of pollutants. Different values for the model constant C{sub {phi}} in the IEM model are tested. The numerical results for the gas velocity, the gas temperature, and the mass fraction of methanol vapor are compared with experimental data in the literature. Good agreement with experiment is obtained when C{sub {phi}}=2.0. Marginal PDFs of mixture fraction, enthalpy, and gas temperature are presented. The computed PDFs of mixture fraction are compared with the presumed standard {beta} function and modified {beta} function. The results show that the standard {beta} function fails to reproduce bimodal shapes observed in transported PDF computation, while the modified {beta} function, fits the computed PDFs very well. Moreover, joint PDFs of mixture fraction and enthalpy are presented and analyzed. The enthalpy and mixture fraction are strongly correlated. The samples that deviate from the linear correlation are due to the energy consumption of local spray evaporation. (author)

  2. ASSESSMENT OF SUBSURFACE FATE OF MONOETHANOLAMINE AT SOUR GAS PROCESSING PLANT SITES-PHASE III

    SciTech Connect

    James A. Sorensen

    1999-02-01

    Alkanolamines are commonly used by the natural gas industry to remove hydrogen sulfide, carbon dioxide, and other acid gases from the natural gas in which they occur (''sour'' gas if hydrogen sulfide is present). At sour gas-processing plants, as at all plants that use alkanolamines for acid gas removal (AGR), spills and on-site management of wastes containing alkanolamines and associated reaction products have occasionally resulted in subsurface contamination that is presently the focus of some environmental concern. In 1994, the Energy and Environmental Research Center (EERC) initiated a three-phase program to investigate the natural attenuation processes that control the subsurface transport and fate of the most commonly used alkanolamine in Canada, monoethanolamine (MEA). Funding for the MEA research program was provided by the U.S. Department of Energy (DOE), Canadian Association of Petroleum Producers (CAPP), Canadian Occidental Petroleum Ltd. (CanOxy), Gas Research Institute (GRI), Environment Canada, and the National Energy Board of Canada. The MEA research program focused primarily on examining the biodegradability of MEA and MEA-related waste materials in soils and soil-slurries under a variety of environmentally relevant conditions, evaluating the mobility of MEA in soil and groundwater and the effectiveness of bioremediation techniques for removing contaminants and toxicity from MEA-contaminated soil. The presently inactive Okotoks sour gas-processing plant, owned by CanOxy in Alberta, Canada, was the source of samples and field data for much of the laboratory-based experimental work and was selected to be the location for the field-based efforts to evaluate remediation techniques. The objective of the research program is to provide the natural gas industry with ''real world'' data and insights developed under laboratory and field conditions regarding the effective and environmentally sound use of biological methods for the remediation of soil

  3. Gas engine heat pump system and component efficiency and reliability improvement, phase 1

    NASA Astrophysics Data System (ADS)

    1987-01-01

    The Gas Research Institute is directing several research projects to develop gas fired heat pumps for residential and light commercial use. The project work discussed in the report identifies and evaluates potential improvements in the cycle and key components of these heat pumps and provides short- and long-term inputs for the heat pump product development efforts. Principal results of Phase I studies under the project are: test procedures for gas fired heat pumps (GFHP), a cycle analysis model for GFHP's, an assessment of appropriate compressor technology for GFHP's, specification of fan operating strategies, a review of emission standards for GFHP's, identification of low-temperature capacity enhancement issues, a guide on the sizing of field tests, current assessments of foreign technology valuable to GFHP's, and an assessment of the health and safety attributes of methylene chloride.

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

    PubMed

    Watanabe, Hiroshi; Ito, Nobuyasu; Hu, Chin-Kun

    2012-05-28

    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. PMID:22667535

  5. Sulfur Transfer via Gas Phase in Iron-making Blast Furnace under Intensive Coal Injection

    NASA Astrophysics Data System (ADS)

    Yoshiyuki, Matsui; Rikizou, Tadai; Kenji, Ito; Tadasu, Matsuo; Korehito, Kadoguchi; Reiji, Ono

    The steel industry will move toward more value additive products in the future. In order to support the value additive steel products, iron sources have to be secured with stable operation of furnaces and control of furnace have to be evolved. Environment consciousness including CO2 reduction leads more toward lower reducing agents ratio operation. It is common technical issue on both the more value additive products the environment consciousness to control the sulfur in the hot metal, slag and gas phase.In the present study, the amount of sulfur gasification was measured by combustion experiments with the attention on the simultaneous gasification of sulfur with carbon. By description of sulfurization from gas to burden materials based on the temperature distribution measured in actual furnace, the amount of sulfur transferred to gas was evaluated.

  6. Analysis of organic gas phase compounds formed by hydrothermal liquefaction of Dried Distillers Grains with Solubles.

    PubMed

    Madsen, René B; Christensen, Per S; Houlberg, Kasper; Lappa, Elpiniki; Mørup, Anders J; Klemmer, Maika; Olsen, Eva M; Jensen, Mads M; Becker, Jacob; Iversen, Bo B; Glasius, Marianne

    2015-09-01

    This work provides a comprehensive characterization of the gas phase from hydrothermal liquefaction of Dried Distillers Grains with Solubles (DDGS) collected during a 24-h continuous experiment. The gas consisted mainly of CO2, CO, H2, CH4 and C2H6 accounting for 96 v/v% while further analysis by gas chromatography coupled to mass spectrometry (GC-MS) showed additionally 62 compounds of which 54 were tentatively identified. These products included methanethiol, dimethyl sulfide, various olefins and several aromatic compounds. The composition provided clear indication of the steady state of the system. Apart from CO2, olefins were the most abundant compound class and could provide a source of revenue. PMID:26051525

  7. Detection of unknown gas-phase chemical plumes in hyperspectral imagery

    NASA Astrophysics Data System (ADS)

    Theiler, James; Wohlberg, Brendt

    2013-05-01

    Gas-phase chemical plumes exhibit, particularly in the infrared, distinctive emission signatures as a function of wavelength. Hyperspectral imagery can exploit this distinctiveness to detect specific chemicals, even at low concentrations, using matched filters that are tailored both the the specific structure of the chemical signature and to the statistics of the background clutter. But what if the chemical species is unknown? One can apply matched filters to a long list of candidate chemicals (or chemical mixtures), or one can treat the problem as one of anomaly detection. In this case, however, the anomalous signals of interest are not completely unknown. Gas spectra are generically sparse (absorbing or emitting at only a few wavelengths), and this property can be exploited to enhance the sensitivity of anomaly detection algorithms. This paper investigates the utility of sparse signal anomaly detection for the problem of finding plumes of gas with unknown chemistry in hyperspectral imagery.

  8. Microwave detection of the primary ozonide of ethylene in the gas phase

    NASA Astrophysics Data System (ADS)

    Zozom, J.; Gillies, C. W.; Suenram, R. D.; Lovas, F. J.

    1987-09-01

    The primary ozonide of ethylene ? has been observed and studied in the gas phase for the first time. A specially designed low-temperature absorption cell was employed in which the primary ozonide was prepared in situ by the low-temperature reaction of ozone with ethylene. An assignment of the rotational spectrum and electric dipole moment measurements have established the oxygen envelope conformation (C s symmetry) to the lowest-energy form for this elusive chemical species.

  9. GAS PHASE MOLECULAR DYNAMICS: HIGH-RESOLUTION SPECTROSCOPIC PROBES OF CHEMICAL DYNAMICS.

    SciTech Connect

    HALL, G.E.

    2006-05-30

    This research is carried out as part of the Gas Phase Molecular Dynamics group program in the Chemistry Department at Brookhaven National Laboratory. High-resolution spectroscopic tools are developed and applied to problems in chemical dynamics. Recent topics have included the state-resolved studies of collision-induced electronic energy transfer, dynamics of barrierless unimolecular reactions, and the kinetics and spectroscopy of transient species.

  10. a Nucleoside Under Observation in the Gas Phase: a Rotational Study of Uridine

    NASA Astrophysics Data System (ADS)

    Peña, Isabel; Alonso, José L.

    2014-06-01

    The nucleoside of uridine has been placed in the gas phase by laser ablation and the most stable C2{'}-anti conformation characterized by broadband chirped pulse (CP-FTMW) and narrowband molecular beam Fourier transform microwave (LA-MB-FTMW) spectroscopies. The quadrupole hyperfine structure, originated by two 14N nuclei, has been completely resolved. Intramolecular hydrogen bonds involving uracil and ribose moieties have been found to play an important role in the stabilization of the nucleoside.

  11. Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes

    NASA Astrophysics Data System (ADS)

    Lee, Anita; Goldstein, Allen H.; Keywood, Melita D.; Gao, Song; Varutbangkul, Varuntida; Bahreini, Roya; Ng, Nga L.; Flagan, Richard C.; Seinfeld, John H.

    2006-04-01

    The ozonolyses of six monoterpenes (α-pinene, β-pinene, 3-carene, terpinolene, α-terpinene, and myrcene), two sesquiterpenes (α-humulene and β-caryophyllene), and two oxygenated terpenes (methyl chavicol and linalool) were conducted individually in Teflon chambers to examine the gas-phase oxidation product and secondary organic aerosol (SOA) yields from these reactions. Particle size distribution and number concentration were monitored and allowed for the calculation of the SOA yield from each experiment, which ranged from 1 to 54%. A proton transfer reaction mass spectrometer (PTR-MS) was used to monitor the evolution of gas-phase products, identified by their mass to charge ratio (m/z). Several gas-phase oxidation products, formaldehyde, acetaldehyde, formic acid, acetone, acetic acid, and nopinone, were identified and calibrated. Aerosol yields, and the yields of these identified and calibrated oxidation products, as well as many higher m/z oxidation products observed with the PTR-MS, varied significantly between the different parent terpene compounds. The sum of measured oxidation products in the gas and particle phase ranged from 33 to 77% of the carbon in the reacted terpenes, suggesting there are still unmeasured products from these reactions. The observations of the higher molecular weight oxidation product ions provide evidence of previously unreported compounds and their temporal evolution in the smog chamber from multistep oxidation processes. Many of the observed ions, including m/z 111 and 113, have also been observed in ambient air above a Ponderosa pine forest canopy, and our results confirm they are consistent with products from terpene + O3 reactions. Many of these products are stable on the timescale of our experiments and can therefore be monitored in field campaigns as evidence for ozone oxidative chemistry.

  12. The effect of molecular dynamics sampling on the calculated observable gas-phase structures.

    PubMed

    Tikhonov, Denis S; Otlyotov, Arseniy A; Rybkin, Vladimir V

    2016-07-21

    In this study, we compare the performance of various ab initio molecular dynamics (MD) sampling methods for the calculation of the observable vibrationally-averaged gas-phase structures of benzene, naphthalene and anthracene molecules. Nose-Hoover (NH), canonical and quantum generalized-Langevin-equation (GLE) thermostats as well as the a posteriori quantum correction to the classical trajectories have been tested and compared to the accurate path-integral molecular dynamics (PIMD), static anharmonic vibrational calculations as well as to the experimental gas electron diffraction data. Classical sampling methods neglecting quantum effects (NH and canonical GLE thermostats) dramatically underestimate vibrational amplitudes for the bonded atom pairs, both C-H and C-C, the resulting radial distribution functions exhibit nonphysically narrow peaks. This deficiency is almost completely removed by taking the quantum effects on the nuclei into account. The quantum GLE thermostat and a posteriori correction to the canonical GLE and NH thermostatted trajectories capture most vibrational quantum effects and closely reproduce computationally expensive PIMD and experimental radial distribution functions. These methods are both computationally feasible and accurate and are therefore recommended for calculations of the observable gas-phase structures. A good performance of the quantum GLE thermostat for the gas-phase calculations is encouraging since its parameters have been originally fitted for the condensed-phase calculations. Very accurate molecular structures can be predicted by combining the equilibrium geometry obtained at a high level of electronic structure theory with vibrational amplitudes and corrections calculated using MD driven by a lower level of electronic structure theory. PMID:27331660

  13. Gas-Phase Neutral Binary Oxide Clusters: Distribution, Structure, and Reactivity toward CO.

    PubMed

    Wang, Zhe-Chen; Yin, Shi; Bernstein, Elliot R

    2012-09-01

    Neutral binary (vanadium-cobalt) oxide clusters are generated and detected in the gas phase for the first time. Their reactivities toward carbon monoxide (CO) are studied both experimentally and theoretically. Experimental results suggest that neutral VCoO4 can react with CO to generate VCoO3 and CO2. Density functional theory studies show parallel results as well as provide detailed reaction mechanisms. PMID:26292125

  14. Comparison of ozone determinations by ultraviolet photometry and gas-phase titration

    NASA Technical Reports Server (NTRS)

    Demore, W. B.; Patapoff, M.

    1976-01-01

    A comparison of ozone determinations based on ultraviolet absorption photometry and gas-phase titration (GPT) shows good agreement between the two methods. Together with other results, these findings indicate that three candidate reference methods for ozone, UV photometry, IR photometry, and GPT are in substantial agreement. However, the GPT method is not recommended for routine use by air pollution agencies for calibration of ozone monitors because of susceptibility to experimental error.

  15. Organic molecules in ices and their release into the gas phase

    NASA Astrophysics Data System (ADS)

    Fayolle, Edith; Oberg, Karin I.; Garrod, Robin; van Dishoeck, Ewine; Rajappan, Mahesh; Bertin, Mathieu; Romanzin, Claire; Michaut, Xavier; Fillion, Jean-Hugues

    2015-08-01

    Organic molecules in the early stages of star formation are mainly produced in icy mantles surrounding interstellar dust grains. Identifying these complex organics and quantifying their abundance during the evolution of young stellar objects is of importance to understand the emergence of life. Simple molecules in ices, up to methanol in size, have been identified in the interstellar medium through their mid-IR vibrations, but band confusion prevents detections of more complex and less abundant organic molecules in interstellar ices. The presence of complex organics on grains can instead be indirectly inferred from observations of their rotational lines in the gas phase following ice sublimation.Thermal sublimation of protostellar ices occurs when icy grains flow toward a central protostar, resulting in the formation of a hot-core or a hot-corinos. The high degree of chemical complexity observed in these dense and warm regions can be the results of i) direct synthesis on the grains followed by desorption, but also to ii) the desorption of precursors from the ice followed by gas-phase chemistry. I will show how spatially resolved millimetric observations of hot cores and cooler protostellar environments, coupled to ice observations can help us pinpoint the ice or gas-phase origin of these organic species.Organic molecules have also recently been observed in cold environments where thermal desorption can be neglected. The presence of these cold molecules in the gas phase is most likely due to non-thermal desorption processes induced by, for e.g., photon-, electron-, cosmic-ray-irradiation, shock, exothermic reactions... I will present laboratory and observational efforts that push our current understanding of these non-thermal desorption processes and how they could be use to quantify the amount of organics in ices.

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

    SciTech Connect

    Connolly, M.J.; Liekhus, K.J.; Djordjevic, S.M.; Loehr, C.A.; Spangler, L.R.

    1998-06-01

    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.

  17. Position for determining gas phase volatile organic compound concentrations in transuranic waste containers. Revision 1

    SciTech Connect

    Connolly, M.J.; Liekhus, K.J.; Djordjevic, S.M.; Loehr, C.A.; Spangler, L.R.

    1995-08-01

    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 Laboratory (INEL) 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 INEL 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.

  18. Method and apparatus for selective capture of gas phase analytes using metal .beta.-diketonate polymers

    DOEpatents

    Harvey, Scott D [Kennewick, WA

    2011-06-21

    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.

  19. Cryogenic Ion Mobility-Mass Spectrometry: Tracking Ion Structure from Solution to the Gas Phase.

    PubMed

    Servage, Kelly A; Silveira, Joshua A; Fort, Kyle L; Russell, David H

    2016-07-19

    Electrospray ionization (ESI) combined with ion mobility-mass spectrometry (IM-MS) is adding new dimensions, that is, structure and dynamics, to the field of biological mass spectrometry. There is increasing evidence that gas-phase ions produced by ESI can closely resemble their solution-phase structures, but correlating these structures can be complicated owing to the number of competing effects contributing to structural preferences, including both inter- and intramolecular interactions. Ions encounter unique hydration environments during the transition from solution to the gas phase that will likely affect their structure(s), but many of these structural changes will go undetected because ESI-IM-MS analysis is typically performed on solvent-free ions. Cryogenic ion mobility-mass spectrometry (cryo-IM-MS) takes advantage of the freeze-drying capabilities of ESI and a cryogenically cooled IM drift cell (80 K) to preserve extensively solvated ions of the type [M + xH](x+)(H2O)n, where n can vary from zero to several hundred. This affords an experimental approach for tracking the structural evolution of hydrated biomolecules en route to forming solvent-free gas-phase ions. The studies highlighted in this Account illustrate the varying extent to which dehydration can alter ion structure and the overall impact of cryo-IM-MS on structural studies of hydrated biomolecules. Studies of small ions, including protonated water clusters and alkyl diammonium cations, reveal structural transitions associated with the development of the H-bond network of water molecules surrounding the charge carrier(s). For peptide ions, results show that water networks are highly dependent on the charge-carrying species within the cluster. Specifically, hydrated peptide ions containing lysine display specific hydration behavior around the ammonium ion, that is, magic number clusters with enhanced stability, whereas peptides containing arginine do not display specific hydration around the

  20. Thermal phase transitions in a honeycomb lattice gas with three-body interactions.

    PubMed

    Lohöfer, Maximilian; Bonnes, Lars; Wessel, Stefan

    2013-11-01

    We study the thermal phase transitions in a classical (hard-core) lattice gas model with nearest-neighbor three-body interactions on the honeycomb lattice, based on parallel tempering Monte Carlo simulations. This system realizes incompressible low-temperature phases at fractional fillings of 9/16, 5/8, and 3/4 that were identified in a previous study of a related quantum model. In particular, both the 9/16 and the 5/8 phase exhibit an extensive ground-state degeneracy reflecting the frustrated nature of the three-body interactions on the honeycomb lattice. The thermal melting of the 9/16 phase is found to be a first-order, discontinuous phase transition. On the other hand, from the thermodynamic behavior we obtain indications for a four-states Potts-model thermal transition out of the 5/8 phase. We find that this thermal Potts-model transition relates to the selection of one out of four extensive sectors within the low-energy manifold of the 5/8 phase, which we obtain via an exact mapping of the ground-state manifold to a hard-core dimer model on an embedded honeycomb superlattice. PMID:24329242