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Sample records for air n2 o2

  1. Fundamental Insulation Characteristics of Air, N2, CO2, N2/O2 and SF6/N2 Mixed Gases

    NASA Astrophysics Data System (ADS)

    Rokunohe, Toshiaki; Yagihashi, Yoshitaka; Endo, Fumihiro; Oomori, Takashi

    SF6 gas has excellent dielectric strength and interruption performance. For these reasons, it has been widely used for gas insulated switchgear (GIS). However, use of SF6 gas has become regulated under agreements set at the 1997 COP3. Presently, development of a gas circuit breaker (GCB) using CO2 gas and development of a high voltage vacuum circuit breaker (VCB) are being pursued. GIS consists of disconnectors (DS), earthing switches (ES) and buses in addition to GCB. Since the interruption performance is not an important requirement for DS, ES and BUS, use of a gas with high dielectric strength is better than use of a gas with good interruption performance. Air and N2 are not greenhouse gases, and their dielectric strengths are higher than those of other SF6 alternative gases, but only about one-third of the dielectric strength of SF6 gas. This paper deals with a suitable insulation gas which has no greenhouse effect as an SF6 alternative gas. The N2/O2 mixed gas was investigated by changing the ratio of O2. Moreover, the effect of an insulation coating was investigated and compared with the dielectric strength of SF6/N2 mixed gas. The dielectric strength of air under the coating condition was equal to that of 10%SF6/N2 mixed gas.

  2. Orbital tuning of deep ice cores using O2/N2 of trapped air

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Aoki, S.; Nakazawa, T.

    2014-12-01

    The chronology of the first Dome Fuji deep ice core (80,000-340,000 yr BP) was established by orbital tuning of measured O2/N2 ratios in trapped air to the past local summer insolation at the drill site (Kawamura et al., 2007). The O2/N2 ratios found in ice cores are generally lower than atmospheric ratio because of size-dependent molecular fractionation during bubble close-off. The magnitude of this gas fractionation appears to be influenced by snow metamorphism when the layer was originally at the surface, which in turn is controlled by local summer insolation (Fujita et al., 2009). The O2/N2 record has little 100,000-yr periodicity (strongest in climatic records), suggesting insignificant climatic influence in the orbital tuning. Agreement of the O2/N2 chronology with U-Th radiometric chronology of speleothems (within ~2000 yr) suggests that O2/N2 and summer insolation are indeed in phase. However, it may not be common to all ice cores that O2/N2 signal only records local summer insolation. For example, the GISP2 ice core (Greenland) has clear imprint of abrupt climate changes in the O2/N2 record, indicating climatic (non-insolation) signal in the record and the possibility of phase variability of O2/N2 relative to the past insolation (Suwa and Bender, 2008). Here we present new O2/N2 record from the second Dome Fuji ice core with significant improvements in ice core storage practice and mass spectrometry. In particular, the ice core had been stored at about -50 ˚C until the air extraction except during transportations, which prevent fractionation due to gas loss during the core storage. The precision of the new O2/N2 data set is improved by a factor of 3 over the previous data, and we do not observe outliers (there were 15% outliers in the previous data). Clear imprint of local insolation is recognizable in the new O2/N2, which would enable us to generate a chronology with accuracy of ~2000 yr towards older periods. Samples from the first core after long

  3. Accurate age scale of the Dome Fuji ice core, Antarctica from O2/N2 ratio of trapped air

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Aoki, S.; Nakazawa, T.; Suzuki, K.; Parrenin, F.

    2012-04-01

    Chronology of the first Dome Fuji deep ice core (core length: 2,500 m, ice thickness: 3,035 m) for the age range from 80 kyr to 340 kyr ago was established by orbital tuning of measured O2/N2 ratios in trapped air to local summer insolation, with precision better than about 2,000 years (Kawamura et al., 2007). The O2/N2 ratios found in polar ice cores are slightly lower than the atmospheric ratio because of size-dependent molecular fractionation during bubble close-off. The magnitude of this gas fractionation is believed to be governed by the magnitude of snow metamorphism when the layer was originally at the surface, which in turn is controlled by local summer insolation (Fujita et al., 2009). A strong advantage of the O2/N2 chronology is that there is no need to assume a lag between climatic records in the ice core and orbital forcings, becacuse O2/N2 ratios record local insolation through physical processes. Accuracy of the chronology was validated by comparing the O2/N2 chronology with U-Th radiometric chronology of speleothem records (Cheng et al., 2009) for the ends of Terminations II, III and IV, as well as several large climatic events, for which both ice-core CH4 and speleothem δ18O (a proxy for precipitation) show abrupt shifts as seen in the last glacial period. All ages from O2/N2 and U-Th chronology agreed with each other within ~2,000 yr. The O2/N2 chronology permits comparisons between Antarctic climate, greenhouse gases, astronomically calculated orbital parameters, and radiometrically-dated sea level and monsoon records. Here, we completed the measurements of O2/N2 ratios of the second Dome Fuji ice core, which reached bedrock, for the range from 2,400 to 3,028 m (320 - 700 kyr ago) at approximately 2,000-year time resolution. We made significant improvements in ice core storage practices and mass spectrometry. In particular, the ice core samples were stored at about -50 ° C until the air extraction, except during short periods of transportation

  4. Inactivation of Escherichia coli Cells in Aqueous Solution by Atmospheric-Pressure N2, He, Air, and O2 Microplasmas

    PubMed Central

    Zhou, Renwu; Zhang, Xianhui; Bi, Zhenhua; Zong, Zichao; Niu, Jinhai; Song, Ying; Yang, Size

    2015-01-01

    Atmospheric-pressure N2, He, air, and O2 microplasma arrays have been used to inactivate Escherichia coli cells suspended in aqueous solution. Measurements show that the efficiency of inactivation of E. coli cells is strongly dependent on the feed gases used, the plasma treatment time, and the discharge power. Compared to atmospheric-pressure N2 and He microplasma arrays, air and O2 microplasma arrays may be utilized to more efficiently kill E. coli cells in aqueous solution. The efficiencies of inactivation of E. coli cells in water can be well described by using the chemical reaction rate model, where reactive oxygen species play a crucial role in the inactivation process. Analysis indicates that plasma-generated reactive species can react with E. coli cells in water by direct or indirect interactions. PMID:26025895

  5. Inactivation of Escherichia coli Cells in Aqueous Solution by Atmospheric-Pressure N2, He, Air, and O2 Microplasmas.

    PubMed

    Zhou, Renwu; Zhang, Xianhui; Bi, Zhenhua; Zong, Zichao; Niu, Jinhai; Song, Ying; Liu, Dongping; Yang, Size

    2015-08-01

    Atmospheric-pressure N2, He, air, and O2 microplasma arrays have been used to inactivate Escherichia coli cells suspended in aqueous solution. Measurements show that the efficiency of inactivation of E. coli cells is strongly dependent on the feed gases used, the plasma treatment time, and the discharge power. Compared to atmospheric-pressure N2 and He microplasma arrays, air and O2 microplasma arrays may be utilized to more efficiently kill E. coli cells in aqueous solution. The efficiencies of inactivation of E. coli cells in water can be well described by using the chemical reaction rate model, where reactive oxygen species play a crucial role in the inactivation process. Analysis indicates that plasma-generated reactive species can react with E. coli cells in water by direct or indirect interactions. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

  6. Air-sea CO2, O2 and N2O fluxes in the Namibian Upwelling System: a modelling approach

    NASA Astrophysics Data System (ADS)

    Gutknecht, Elodie; Dadou, Isabelle; Cambon, Gildas; Sudre, Joel; Garcon, Veronique

    2010-05-01

    Uncertainties exist in our understanding of the biogeochemical cycles of nitrogen and carbon, two key cycles for climate regulation via both greenhouse gases N2O and CO2. The role of the Benguela Upwelling System as a nitrogen source for the open ocean, via the turbulent instabilities and filament structures enriched in chlorophyll, is still to be investigated. The loss of nitrogen by denitrification and/or anammox with CO2, N2O and H2S gas emissions can also occur in this very productive zone in which dissolved oxygen concentrations may get very low. A 3D coupled hydrodynamical (ROMS) and biogeochemical (BioBUS) model which takes into account these important processes is used in the Namibian Upwelling System, forced by climatological forcing. Air-sea gas fluxes are estimated based on Wanninkhof (1992)'s relationship for air-sea gas transfer velocity and QuickSCAT wind field. A significant evasion flux of CO2 out of the ocean occurs all year round, in the upwelling region between 20°S and 26°S with a marked spatial heterogeneity. The period of strong upwelling can induce outgoing CO2 fluxes up to 8.7 molCO2 m-2 yr-1 along the coast, while during the weak upwelling period the CO2 flux to the atmosphere remains close to 4.4 molCO2 m-2 yr-1. The whole studied domain represents a net annual source of CO2 for the atmosphere (3.5 molCO2 m-2 yr-1). Modelled oxygen concentrations vary between 4.5 ml.l-1 and 6 ml.l-1 over a year in Walvis Bay (23°S - 14°E) at the surface, and between 1.5 ml.l-1 and 3 ml.l-1 at 100 m depth. These estimations are in agreement with observations at the Walvis Bay station (23°S - 14°E). An important air-sea O2 flux to the ocean (up to 80 molO2.m-2.yr-1) is observed close to the coast as compared to offshore values (~1 molO2.m-2.yr-1). Due to denitrification on the continental shelf, the Walvis Bay area can potentially be a net source of N2O for the atmosphere. N2O concentrations are estimated from oxygen using different parameterisations

  7. Characteristics of surface-wave plasma with air-simulated N2 O2 gas mixture for low-temperature sterilization

    NASA Astrophysics Data System (ADS)

    Xu, L.; Nonaka, H.; Zhou, H. Y.; Ogino, A.; Nagata, T.; Koide, Y.; Nanko, S.; Kurawaki, I.; Nagatsu, M.

    2007-02-01

    Sterilization experiments using low-pressure air discharge plasma sustained by the 2.45 GHz surface-wave have been carried out. Geobacillus stearothermoplilus spores having a population of 3.0 × 106 were sterilized for only 3 min using air-simulated N2-O2 mixture gas discharge plasma, faster than the cases of pure O2 or pure N2 discharge plasmas. From the SEM analysis of plasma-irradiated spores and optical emission spectroscopy measurements of the plasmas, it has been found that the possible sterilization mechanisms of air-simulated plasma are the chemical etching effect due to the oxygen radicals and UV emission from the N2 molecules and NO radicals in the wavelength range 200-400 nm. Experiment suggested that UV emission in the wavelength range less than 200 nm might not be significant in the sterilization. The UV intensity at 237.0 nm originated from the NO γ system (A 2Σ+ → X 2Π) in N2-O2 plasma as a function of the O2 percentage added to N2-O2 mixture gas has been investigated. It achieved its maximum value when the O2 percentage was roughly 10-20%. This result suggests that air can be used as a discharge gas for sterilization, and indeed we have confirmed a rapid sterilization with the actual air discharge at a sample temperature of less than 65 °C.

  8. Close Resemblance Between Local Summer Insolation, O2/N2 and Total Air Content from the Dome Fuji Ice Core, Antarctica

    NASA Astrophysics Data System (ADS)

    Kawamura, K.; Nakazawa, T.; Aoki, S.; Fujii, Y.; Watanabe, O.; Severinghaus, J. P.

    2004-12-01

    O2/N2 ratio from ice cores has shown depleted values compared to the atmosphere due to selective exclusion of O2 during bubble formation at the base of firn. The long record from the Vostok ice core revealed that O2/N2 ratio records the local summer insolation. Insolation may affect physical properties of the firn near the surface, which later determines how much O2/N2 is fractionated the during bubble close-off process. We present here a supportive record of O2/N2 ratio for the last 340 kyr along the Dome Fuji ice core, Antarctica, which shows variations similar to the summer insolation at 77° S. Moreover, the variation of total air content (TAC) in the Dome Fuji core resembles that of O2/N2. High TAC and high O2/N2 ratio appear at times of low summer insolation. Since the TAC variation is too large to be explained by the elevation change at the Dome Fuji site in the past, a possible cause is variation of the so-called ``lock-in zone'' thickness on the orders of several meters. The lock-in zone is a region 0-10 m thick at the bottom of firn where horizontal impermeable layers prevent vertical gas mixing. At times of low insolation, the firn would retain inhomogeneities such as wind crusts and high-density layers. These small-scale inhomogeneities do not affect bulk density very much but may help trap the gases at a lower bulk density (and higher porosity and thus TAC) through formation of a thicker lock-in zone than in times of high insolation. High insolation would homogenize the firn structure through recrystallization. O2/N2 ratio would be less depleted if there is a lock-in zone within the total close-off zone, because O2 molecules once excluded from bubbles would eventually be re-trapped in the ice in the lock-in zone.

  9. Air-, N2-, and O2-broadening and shift coefficients in the nu(3) spectral region of (C-12)H4

    NASA Technical Reports Server (NTRS)

    Benner, D. C.; Devi, V. M.; Smith, Mary A. H.; Rinsland, Curtis P.

    1993-01-01

    Results are presented of an analysis of 29 room-temperature laboratory absorption spectra of a dilute CH4 sample in dry air, N2, and O2 at total pressures ranging from 60 to 550 torr, yielding values of pressure-broadening and pressure-induced-shift coefficients for more than 450 vibration-rotation transitions in the nu(3), nu(2) + nu(4), and 2nu(2)-super-2 bands of (C-12)H4. Comparisons of the present results for the nu(3) and nu(2) + nu(4) bands with previous measurements on other bands and isotopes of CH4 show that, for a given transition, broadening by air and N2 are nearly equal, and broadening by O2 is smaller by less than 10 percent. It is also found that the pressure shift coefficients are more vibrational dependent than the pressure broadening coefficients.

  10. Space and time analysis of the nanosecond scale discharges in atmospheric pressure air: I. Gas temperature and vibrational distribution function of N2 and O2

    NASA Astrophysics Data System (ADS)

    Lo, A.; Cessou, A.; Boubert, P.; Vervisch, P.

    2014-03-01

    Reliable experimental data on nanosecond discharge plasmas in air become more and more crucial considering their interest in a wide field of applications. However, the investigations on such nonequilibrium plasmas are made difficult by the spatial non-homogeneities, in particular under atmospheric pressure, the wide range of time scales, and the complexity of multi-physics processes involved therein. In this study, we report spatiotemporal experimental analysis on the gas temperature and the vibrational excitation of N2 and O2 in their ground electronic state during the post-discharge of an overvoltage nanosecond-pulsed discharge generated in a pin-to-plane gap of air at atmospheric pressure. The gas temperature during the pulsed discharge is measured by optical emission spectroscopy related to the rotational bands of the 0-0 vibrational transition N2(C 3 Πu, v = 0) → N2(B3 Πg, v = 0) of nitrogen. The results show a rapid gas heating up to 700 K in tens of nanoseconds after the current rise. This fast gas heating leads to a high gas temperature up to 1000 K measured at 150 ns in the first stages of the post-discharge using spontaneous Raman scattering (SRS). The spatiotemporal measurements of the gas temperature and the vibrational distribution function of N2 and O2, also obtained by SRS, over the post-discharge show the spatial expansion of the high vibrational excitation of N2, and the gas heating during the post-discharge. The present measurements, focused on thermal and energetic aspect of the discharge, provide a base for spatiotemporal analysis of gas number densities of N2, O2 and O atoms and hydrodynamic effects achieved during the post-discharge in part II of this investigation. All these results provide space and time database for the validation of plasma chemical models for nanosecond-pulsed discharges at atmospheric pressure air.

  11. Effects of Atmospheric-Pressure N2, He, Air, and O2 Microplasmas on Mung Bean Seed Germination and Seedling Growth.

    PubMed

    Zhou, Renwu; Zhou, Rusen; Zhang, Xianhui; Zhuang, Jinxing; Yang, Size; Bazaka, Kateryna; Ken Ostrikov, Kostya

    2016-09-01

    Atmospheric-pressure N2, He, air, and O2 microplasma arrays have been used to investigate the effects of plasma treatment on seed germination and seedling growth of mung bean in aqueous solution. Seed germination and growth of mung bean were found to strongly depend on the feed gases used to generate plasma and plasma treatment time. Compared to the treatment with atmospheric-pressure O2, N2 and He microplasma arrays, treatment with air microplasma arrays was shown to be more efficient in improving both the seed germination rate and seedling growth, the effect attributed to solution acidification and interactions with plasma-generated reactive oxygen and nitrogen species. Acidic environment caused by air discharge in water may promote leathering of seed chaps, thus enhancing the germination rate of mung bean, and stimulating the growth of hypocotyl and radicle. The interactions between plasma-generated reactive species, such as hydrogen peroxide (H2O2) and nitrogen compounds, and seeds led to a significant acceleration of seed germination and an increase in seedling length of mung bean. Electrolyte leakage rate of mung bean seeds soaked in solution activated using air microplasma was the lowest, while the catalase activity of thus-treated mung bean seeds was the highest compared to other types of microplasma.

  12. Effects of Atmospheric-Pressure N2, He, Air, and O2 Microplasmas on Mung Bean Seed Germination and Seedling Growth

    PubMed Central

    Zhou, Renwu; Zhou, Rusen; Zhang, Xianhui; Zhuang, Jinxing; Yang, Size; Bazaka, Kateryna; (Ken) Ostrikov, Kostya

    2016-01-01

    Atmospheric-pressure N2, He, air, and O2 microplasma arrays have been used to investigate the effects of plasma treatment on seed germination and seedling growth of mung bean in aqueous solution. Seed germination and growth of mung bean were found to strongly depend on the feed gases used to generate plasma and plasma treatment time. Compared to the treatment with atmospheric-pressure O2, N2 and He microplasma arrays, treatment with air microplasma arrays was shown to be more efficient in improving both the seed germination rate and seedling growth, the effect attributed to solution acidification and interactions with plasma-generated reactive oxygen and nitrogen species. Acidic environment caused by air discharge in water may promote leathering of seed chaps, thus enhancing the germination rate of mung bean, and stimulating the growth of hypocotyl and radicle. The interactions between plasma-generated reactive species, such as hydrogen peroxide (H2O2) and nitrogen compounds, and seeds led to a significant acceleration of seed germination and an increase in seedling length of mung bean. Electrolyte leakage rate of mung bean seeds soaked in solution activated using air microplasma was the lowest, while the catalase activity of thus-treated mung bean seeds was the highest compared to other types of microplasma. PMID:27584560

  13. Effects of Atmospheric-Pressure N2, He, Air, and O2 Microplasmas on Mung Bean Seed Germination and Seedling Growth

    NASA Astrophysics Data System (ADS)

    Zhou, Renwu; Zhou, Rusen; Zhang, Xianhui; Zhuang, Jinxing; Yang, Size; Bazaka, Kateryna; (Ken) Ostrikov, Kostya

    2016-09-01

    Atmospheric-pressure N2, He, air, and O2 microplasma arrays have been used to investigate the effects of plasma treatment on seed germination and seedling growth of mung bean in aqueous solution. Seed germination and growth of mung bean were found to strongly depend on the feed gases used to generate plasma and plasma treatment time. Compared to the treatment with atmospheric-pressure O2, N2 and He microplasma arrays, treatment with air microplasma arrays was shown to be more efficient in improving both the seed germination rate and seedling growth, the effect attributed to solution acidification and interactions with plasma-generated reactive oxygen and nitrogen species. Acidic environment caused by air discharge in water may promote leathering of seed chaps, thus enhancing the germination rate of mung bean, and stimulating the growth of hypocotyl and radicle. The interactions between plasma-generated reactive species, such as hydrogen peroxide (H2O2) and nitrogen compounds, and seeds led to a significant acceleration of seed germination and an increase in seedling length of mung bean. Electrolyte leakage rate of mung bean seeds soaked in solution activated using air microplasma was the lowest, while the catalase activity of thus-treated mung bean seeds was the highest compared to other types of microplasma.

  14. Comparison of the effects of room air and N2O + O2 used for ProSeal LMA cuff inflation on cuff pressure and oropharyngeal structure.

    PubMed

    Tekin, Murat; Kati, Ismail; Tomak, Yakup; Yuca, Koksal

    2008-01-01

    This study aimed to evaluate the effects of different inflating gases used for ProSeal LMA (PLMA) cuff inflation on cuff pressure, oropharyngeal structure, and the incidence of sore throat. Eighty patients (American Society of Anesthesiologists; ASA I-II) were randomly divided into two groups. PLMA cuff inflation was achieved with appropriate volumes of 50% N2O + 50% O2 in group I and room air in group II, respectively. When the PLMA was removed, oropharyngeal examination was carried out immediately, using a rigid optical telescope. Patients were asked about sore throat symptoms postoperatively. Cuff pressures were significantly lower in group I, except at the initial pressure measurement. Cuff pressure was positively correlated with the length of the operation in group II, and negatively correlated in group I. PLMA cuff inflation with room air led to increased cuff pressure during the operation, possibly due to the diffusion of N2O into the cuff. We consider that a PLMA cuff inflated with an N2O-O2 mixture is convenient, especially in operations in which N2O has been used.

  15. Measurements and Calculations of the Halfwidth of Two Rotational Transitions of Water Vapor Perturbed by N 2, O 2, and Air

    NASA Astrophysics Data System (ADS)

    Colmont, Jean-Marcel; Priem, Dominique; Wlodarczak, Georges; Gamache, Robert R.

    1999-02-01

    In this paper we report the results of both an experimental and theoretical study of the halfwidths of two transitions of water vapor. Measurements on the lines of the H216O and H218O isotopomers located at 325.1 and 203.4 GHz, respectively, were carried out in the temperature range 300-393 K, with N2and O2as perturbing gases. The foreign-broadening coefficients and their temperature-dependence parameters were determined assuming a Voigt profile and the usual temperature dependence for the halfwidth. The retrieved values are compared to values calculated using the complex semiclassical formalism of Robert and Bonamy. The assumed intermolecular potential is a combination of electrostatic and atom-atom components. This last contribution is defined as the sum of pairwise Lennard-Jones 6-12 interactions between the atoms of H2O and the atoms of the perturbing molecules expanded to eighth order. Also calculated are the pressure-induced shifts of the spectral lines for temperatures from 200 to 400 K. Calculated and experimental results are in good agreement, within ±3.2%, except for the N2-broadening temperature coefficients, for which there are discrepancies as high as 23%. Air-broadening parameters are determined following the classical relation: γ (air) = 0.79γ (N2) + 0.21γ (O2).

  16. Emission characteristics of coal combustion in different O2/N2, O2/CO2 and O2/RFG atmosphere.

    PubMed

    Chen, Jyh-Cherng; Liu, Zhen-Shu; Huang, Jian-Sheng

    2007-04-02

    This study investigates the emission characteristics of CO(2), SO(2) and NOx in the flue gas of coal combustion by varying the compositions and concentrations of feed gas (O(2)/CO(2)/N(2)) and the ratios of recycled flue gas. The differences between O(2)/recycled flue gas (O(2)/RFG) combustion and general air combustion are also discussed. Experimental results indicate that the maximum concentration of CO(2) in O(2)/CO(2) combustion system is 95% as the feed gas is 30% O(2)/70% CO(2). The average concentration of CO(2) in the flue gas of O(2)/CO(2) coal combustion system is higher than 90% and much higher than that of O(2)/N(2) coal combustion system. This high concentration of CO(2) is beneficial for the separation of CO(2) from the flue gas by adsorption or absorption technologies. The maximum concentration of CO(2) in O(2)/N(2) combustion system is only 34% at the feed gas 50% O(2)/50% N(2), the concentration of CO(2) is increased with the concentration of O(2) in feed gas. By O(2)/CO(2) combustion technology, higher concentration of SO(2) is produced as the feed gas is 30% O(2)/70% CO(2) or 40% O(2)/60% CO(2), while higher concentration of NOx is produced as the feed gas is 20% O(2)/80% CO(2) or 50% O(2)/50% CO(2). The mass flow rates of CO(2), SO(2) and NOx in the flue gas are all increased with the ratio of recycled flue gas except for the feed gas 20% O(2)/80% CO(2). The enhanced mass flow rates of air pollutants in such O(2)/RFG combustion system are also beneficial for improving the control efficiencies of air pollution control devices. By O(2)/N(2) combustion technology, higher concentrations of SO(2) and NOx are produced as the feed gas is 21% O(2)/79% N(2). The results also indicate that the formation of NOx in general air combustion system is higher than that in O(2)/RFG or O(2)/CO(2) combustion system.

  17. Time-dependent middle ear pressure changes under general anaesthesia in children: N2O-O2 mixture versus air-oxygen mixture.

    PubMed

    Apan, A; Muluk, N Bayar; Güler, S; Budak, B

    2013-01-01

    The aim of this study was to investigate the effects of N2O-O2 mixture (Inspired O2 30%) on middle ear pressure (MEP) in children compared with the effects of an air-oxygen mixture (Inspired O2 50%). The study included thirty child patients who underwent general anaesthesia for different reasons, with the exception of ENT problems and ear interventions. They were randomly divided into two groups. Group 1 (15 children: 10 male and 5 female) received a N2O-O2 mixture (Inspired O2 30%); and group 2 (15 children: 10 male and 5 female) were given an air-oxygen mixture (Inspired O2 50%). MEP was measured using a portable impedance analyser before the operation (PreO),10 minutes after intubation (10AEn), 30 minutes after intubation (30AEn), 10 minutes before extubation (10BEx), 15 minutes after the operation (PO15), 30 minutes after the operation (PO30), 1 hour after the operation (PO1h) and 6 hours after the operation (PO6h). The pressure and compliance values were the same in groups 1 and 2. The pressure-time graphs for the two groups were different: in Group 2, MEP rose quickly at 10AEn and positive pressure values were seen in the middle ear. MEP then fell rapidly until the end of the surgery and lower and negative pressures (Mean -50 daPa) were observed at PO6h. In Group 1, MEP was elevated at 10AEn and positive pressure was found (but not as high as in Group 2). MEP then fell more slowly. In other words, positive pressure in the middle ear persisted longer and the middle ear was subjected to positive pressure and nitrogen over a longer period. Separate analyses were made in Groups 1 and 2 of pressure differences and of compliance values at eight measurement points using the Friedman test. Differences in pressure values were found to be statistically significant in both Group 1 (p = 0.000) and Group 2 (p = 0.000). In Group 1, all the 10AEn and 30AEn values were significantly higher than the PreO, PO30, PO1h and PO6h values. The 10BEx value was significantly higher

  18. Air-Water Exchange of N2 and O2 from In Situ Measurements in the Subarctic and Subtropical Pacific Oceans: Oxygen Flux and Net Biological Production

    NASA Astrophysics Data System (ADS)

    Emerson, S.

    2008-12-01

    In-situ measurements of wind speed, atmospheric pressure, surface-ocean total dissolved gas pressure and oxygen concentration are used to determine the flux of nitrogen and oxygen between the ocean and atmosphere in the subarctic and subtropical Pacific Oceans. Measurements were made hourly over a period of about one year on surface moorings at the Hawaii Ocean Time series (HOT) in 2005 and at Station P in 2007. Gas pressures in the mixed layer were determined using a gas tension device (GTD) and an oxygen sensor calibrated by Winkler O2 titrations. The pressures of nitrogen and oxygen vary smoothly within a few percent of atmospheric saturation in the subtropical Pacific Ocean, but in the subarctic surface waters these values are punctuated by very rapid excursions caused by storms. The primary flux of oxygen in the upper ocean is between the ocean and atmosphere. We use a simple ocean mixed-layer model to determine this flux and estimate the net biological oxygen production at these sites. Assuming that the net biological oxygen and carbon production are stoichiometrically related over an annual cycle, this method provides a measure of the annual carbon export from the mixed layer, an important component of the ocean's role in the global carbon cycle. There is net biological O2 production most of the year in the subtropical ocean; however, little evidence of net O2 production in the wintertime in the subarctic Pacific. This contrasts with earlier 14C primary production measurements which indicate that wintertime production is about half that in summer at both locations. Annual estimates of biologically produced carbon export at these two sites will be contrasted at the presentation in the fall meeting. This research indicates that it should be possible to derive estimates of the net annual air-water oxygen fluxes caused by biological production at any location of the open ocean where there is a surface mooring. Large, abrupt atmospheric pressure changes (up to 50

  19. Strain-induced extinction of hydrogen-air counterflow diffusion flames - Effects of steam, CO2, N2, and O2 additives to air

    NASA Technical Reports Server (NTRS)

    Pellett, G. L.; Northam, G. B.; Wilson, L. G.

    1992-01-01

    A fundamental study was performed using axisymmetric nozzle and tubular opposed jet burners to measure the effects of laminar plug flow and parabolic input velocity profiles on the extinction limits of H2-air counterflow diffusion flames. Extinction limits were quantified by 'flame strength', (average axial air jet velocity) at blowoff of the central flame. The effects of key air contaminants, on the extinction limits, are characterized and analyzed relative to utilization of combustion contaminated vitiated air in high enthalpy supersonic test facilities.

  20. Strain-induced extinction of hydrogen-air counterflow diffusion flames - Effects of steam, CO2, N2, and O2 additives to air

    NASA Technical Reports Server (NTRS)

    Pellett, G. L.; Northam, G. B.; Wilson, L. G.

    1992-01-01

    A fundamental study was performed using axisymmetric nozzle and tubular opposed jet burners to measure the effects of laminar plug flow and parabolic input velocity profiles on the extinction limits of H2-air counterflow diffusion flames. Extinction limits were quantified by 'flame strength', (average axial air jet velocity) at blowoff of the central flame. The effects of key air contaminants, on the extinction limits, are characterized and analyzed relative to utilization of combustion contaminated vitiated air in high enthalpy supersonic test facilities.

  1. The structure of the O2-N2O complex.

    PubMed

    Salmon, Steven R; Lane, Joseph R

    2015-09-28

    We have investigated the lowest energy structures and interaction energies of the oxygen nitrous oxide complex (O2-N2O) using explicitly correlated coupled cluster theory. We find that the intermolecular potential energy surface of O2-N2O is very flat, with two minima of comparable energy separated by a low energy first order saddle point. Our results are able to conclusively distinguish between the two sets of experimental geometric parameters for O2-N2O that were previously determined from rotationally resolved infrared spectra. The global minimum structure of O2-N2O is therefore found to be planar with a distorted slipped parallel structure. Finally, we show that the very flat potential energy surface of O2-N2O is problematic when evaluating vibrational frequencies with a numerical Hessian and that consideration should be given as to whether results might change if the step-size is varied.

  2. N 2, N 2O and O 2Profiles in a Tagus Estuary Salt Marsh

    NASA Astrophysics Data System (ADS)

    Cartaxana, P.; Lloyd, D.

    1999-06-01

    Vertical gas profiles of N 2, N 2O and O 2were obtained in intact sediment cores from a Tagus estuary salt marsh using membrane inlet mass spectrometry. This technique allows direct measurements of dissolved gas concentrations with minimal disturbance. O 2concentrations decreased sharply with depth, becoming undetectable below 14mm. Denitrification products (N 2and N 2O) occurred in the surface layer of the sediment where O 2was present. Diffusion of N 2and N 2O from the anaerobic zone, denitrification in anaerobic microsites and aerobic denitrification are possible explanations for this observation. N 2was the sole product of denitrification in control sediment cores probably because of the great demand for electron acceptors in this sediment. The addition of NO 3 - and CH 3CO 2 - increased the concentrations of N 2and N 2O in the sediment. Significantly higher concentrations in treated cores occurred between 1·5 and 2·0cm for N 2and between 0·5 and 1·5cm for N 2O. The peak in N 2concentration occurred in the anaerobic zone of the sediment, close to the aerobic-anaerobic interface while the peak in N 2O concentration occurred above this interface where concentrations of O 2were approximately 10μM. This is indicative that, in this sediment, production of N 2O is less sensitive to the presence of O 2than reduction of N 2O to N 2.

  3. O2 Herzberg State Reaction with N2: A Possible Source of Stratospheric N2O

    NASA Technical Reports Server (NTRS)

    Slanger, Tom G.; Copeland, Richard A.

    1997-01-01

    The goal of this one-year investigation was to determine whether N2O is formed in atmospherically significant quantities by the reaction of vibrationally excited levels of the O2((A3 Sigma(sub u)(sup +)) state with nitrogen. O2(A3 Sigma(sub u)(sup +)) is made throughout the upper stratosphere in considerable amounts by solar photoabsorption, and only a very small reactive yield is necessary for this mechanism to be a major N2O source. By long-term 245-252 nm irradiation of O2/N2 mixtures on- and off-resonance with absorption lines in the O2(A3 Sigma(sub u)(sup +) - X3 Sigma(sub g)(sup -)) transition, followed by N2O analysis by frequency-modulated diode laser absorption spectroscopy, we determined an upper limit for the N2O yield of the candidate reaction. This limit, 3 x 10(exp -5), eliminates O2(A3 Sigma(sub u)(sup +)) + N2 as a significant channel for the generation of stratospheric N2O. In further measurements, we established that N2O is stable under our photolysis conditions, showing that the small amounts of ozone generated from the reaction of O2(A) and O2 do not indirectly lead to destruction of N2O.

  4. Air- and N2-Broadening Coefficients and Pressure-Shift Coefficients in the C-12(O2-16) Laser Bands

    NASA Technical Reports Server (NTRS)

    Devi, V. Malathy; Benner, D. Chris; Smith, Mary Ann H.; Rinsland, Curtis P.

    1998-01-01

    In this paper we report the pressure broadening and the pressure-induced line shift coefficients for 46 individual rovibrational lines in both the (12)C(16)O2, 00(sup 0)1-(10(sup 0)0-02(sup 0)0)I, and 00(sup 0)1-(10(sup 0)0-02(sup 0)0)II, laser bands (laser band I centered at 960.959/cm and laser band II centered at 1063.735/cm) determined from spectra recorded with the McMath-Pierce Fourier transform spectrometer. The results were obtained from analysis of 10 long-path laboratory absorption spectra recorded at room temperature using a multispectrum nonlinear least-squares technique. Pressure effects caused by both air and nitrogen have been investigated. The air-broadening coefficients determined in this study agree well with the values in the 1996 HITRAN database; ratios and standard deviations of the ratios of the present air-broadening measurements to the 1996 HITRAN values for the two laser bands are: 1.005(15) for laser band I and 1.005(14) for laser band II. Broadening by nitrogen is 3 to 4% larger than that of air. The pressure-induced line shift coefficients are found to be transition dependent and different for the P- and R-branch lines with same J" value. No noticeable differences in the shift coefficients caused by air and nitrogen were found. The results obtained are compared with available values previously reported in the literature.

  5. Effect of air composition (N2, O2, Ar, and H2O) on CO2 and CH4 measurement by wavelength-scanned cavity ring-down spectroscopy: calibration and measurement strategy

    NASA Astrophysics Data System (ADS)

    Nara, H.; Tanimoto, H.; Tohjima, Y.; Mukai, H.; Nojiri, Y.; Katsumata, K.; Rella, C. W.

    2012-11-01

    We examined potential interferences from water vapor and atmospheric background gases (N2, O2, and Ar), and biases by isotopologues of target species, on accurate measurement of atmospheric CO2 and CH4 by means of wavelength-scanned cavity ring-down spectroscopy (WS-CRDS). Changes of the background gas mole fractions in the sample air substantially impacted the CO2 and CH4 measurements: variation of CO2 and CH4 due to relative increase of each background gas increased as Ar < O2 < N2, suggesting similar relation for the pressure-broadening effects (PBEs) among the background gas. The pressure-broadening coefficients due to variations in O2 and Ar for CO2 and CH4 are empirically determined from these experimental results. Calculated PBEs using the pressure-broadening coefficients are linearly correlated with the differences between the mole fractions of O2 and Ar and their ambient abundances. Although the PBEs calculation showed that impact of natural variation of O2 is negligible on the CO2 and CH4 measurements, significant bias was inferred for the measurement of synthetic standard gases. For gas standards balanced with purified air, the PBEs were estimated to be marginal (up to 0.05 ppm for CO2 and 0.01 ppb for CH4) although the PBEs were substantial (up to 0.87 ppm for CO2 and 1.4 ppb for CH4) for standards balanced with synthetic air. For isotopic biases on CO2 measurements, we compared experimental results and theoretical calculations, which showed excellent agreement within their uncertainty. We derived instrument-specific water correction functions empirically for three WS-CRDS instruments (Picarro EnviroSense 3000i, G-1301, and G-2301), and evaluated the transferability of the water correction function from G-1301 among these instruments. Although the transferability was not proven, no significant difference was found in the water vapor correction function for the investigated WS-CRDS instruments as well as the instruments reported in the past studies

  6. Mixed Matrix Membranes for O2/N2 Separation: The Influence of Temperature

    PubMed Central

    Fernández-Barquín, Ana; Casado-Coterillo, Clara; Valencia, Susana; Irabien, Angel

    2016-01-01

    In this work, mixed matrix membranes (MMMs) composed of small-pore zeolites with various topologies (CHA (Si/Al = 5), LTA (Si/Al = 1 and 5), and Rho (Si/Al = 5)) as dispersed phase, and the hugely permeable poly(1-trimethylsilyl-1-propyne) (PTMSP) as continuous phase, have been synthesized via solution casting, in order to obtain membranes that could be attractive for oxygen-enriched air production. The O2/N2 gas separation performance of the MMMs has been analyzed in terms of permeability, diffusivity, and solubility in the temperature range of 298–333 K. The higher the temperature of the oxygen-enriched stream, the lower the energy required for the combustion process. The effect of temperature on the gas permeability, diffusivity, and solubility of these MMMs is described in terms of the Arrhenius and Van’t Hoff relationships with acceptable accuracy. Moreover, the O2/N2 permselectivity of the MMMs increases with temperature, the O2/N2 selectivities being considerably higher than those of the pure PTMSP. In consequence, most of the MMMs prepared in this work exceeded the Robeson’s upper bound for the O2/N2 gas pair in the temperature range under study, with not much decrease in the O2 permeabilities, reaching O2/N2 selectivities of up to 8.43 and O2 permeabilities up to 4,800 Barrer at 333 K. PMID:27196937

  7. Efficiency of Collisional O2 + N2 Vibrational Energy Exchange.

    PubMed

    Garcia, E; Kurnosov, A; Laganà, A; Pirani, F; Bartolomei, M; Cacciatore, M

    2016-03-03

    By following the scheme of the Grid Empowered Molecular Simulator (GEMS), a new O2 + N2 intermolecular potential, built on ab initio calculations and experimental (scattering and second virial coefficient) data, has been coupled with an appropriate intramolecular one. On the resulting potential energy surface detailed rate coefficients for collision induced vibrational energy exchanges have been computed using a semiclassical method. A cross comparison of the computed rate coefficients with the outcomes of previous semiclassical calculations and kinetic experiments has provided a foundation for characterizing the main features of the vibrational energy transfer processes of the title system as well as a critical reading of the trajectory outcomes and kinetic data. On the implemented procedures massive trajectory runs for the proper interval of initial conditions have singled out structures of the vibrational distributions useful to formulate scaling relationships for complex molecular simulations.

  8. Thermogravimetric analyses of combustion of lignocellulosic materials in N2/O2 and CO2/O2 atmospheres.

    PubMed

    Lai, ZhiYi; Ma, XiaoQian; Tang, YuTing; Lin, Hai; Chen, Yong

    2012-03-01

    The combustion of paper, fruit waste and plant residue mixtures representing the lignocellulosic materials of municipal solid waste (MSW) in different atmospheres (80N(2)/20O(2), 70N(2)/30O(2), 60N(2)/40O(2), 50N(2)/50O(2), 80CO(2)/20O(2), 70CO(2)/30O(2), 60CO(2)/40O(2), 50CO(2)/50O(2)) was analyzed thermogravimetrically. Replacement of 80% N(2) by 80% CO(2) resulted in a slightly later ignition, a lower maximum weight loss rate and a change in reactions occurring above 600°C; however, as the oxygen concentration increased from 20% to 50% in CO(2)/O(2) atmosphere, the ignition temperature decreased from 318.5 to 310.8°C and the maximum weight loss rate increased from 20.82% to 23.57%/min. An oxygen content of 30% in the CO(2)/O(2) atmosphere achieved a similar combustion performance as a 80N(2)/20O(2). The fruit waste mixture had the least residual weight (about 5%) and the earliest ignition (about 220°C). This work contributes to the comprehensive understanding of lignocellulosic materials combustion and development of MSW oxy-fuel combustion.

  9. N2/O2/H2 Dual-Pump Cars: Validation Experiments

    NASA Technical Reports Server (NTRS)

    OByrne, S.; Danehy, P. M.; Cutler, A. D.

    2003-01-01

    The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method is used to measure temperature and the relative species densities of N2, O2 and H2 in two experiments. Average values and root-mean-square (RMS) deviations are determined. Mean temperature measurements in a furnace containing air between 300 and 1800 K agreed with thermocouple measurements within 26 K on average, while mean mole fractions agree to within 1.6 % of the expected value. The temperature measurement standard deviation averaged 64 K while the standard deviation of the species mole fractions averaged 7.8% for O2 and 3.8% for N2, based on 200 single-shot measurements. Preliminary measurements have also been performed in a flat-flame burner for fuel-lean and fuel-rich flames. Temperature standard deviations of 77 K were measured, and the ratios of H2 to N2 and O2 to N2 respectively had standard deviations from the mean value of 12.3% and 10% of the measured ratio.

  10. Discharge Kinetics of N2-O2 Laser Generated Plasma Channels

    NASA Astrophysics Data System (ADS)

    Ladouceur, Harold; Baronavski, Andrew; Petrova, Tzvetelina

    2006-10-01

    We study both experimentally and theoretically the effects of recombination and attachment of different N2--O2 gas compositions upon the plasma channel dynamics at one atmosphere. The time-dependent DC electrical conductivity technique [1] has been applied to determine the electron density decay. The rate constants have been determined from the electron balance equation by curve fitting of voltage-time measurements over the decay time interval. The measured electron density decay time for air is hundreds of nanoseconds while for pure nitrogen it is much longer, about 2 μs. For air, we derive an attachment rate ηair=1.39x10^7;s-1 and an electron-ion recombination rate βair=1.02x10-8;cm^31pts-1. In order to investigate in details the kinetics of N2--O2 gas mixture we developed a time-dependent collisional-radiative model based upon the numerical solution of the electron Boltzmann equation for the electron energy distribution function. It is coupled with the time-dependent balance equations of electrons, atomic and molecular ions under consideration, and various nitrogen and oxygen species in ground and excited states. The validity of the model was verified by comparison of the swarm parameters derived from the model with experimental parameters for pure oxygen, pure nitrogen, and air. [1] H.D. Ladouceur at al., Optics Communications, 189 (2001) 107 * NRL-NRC Postdoc

  11. Nonpolar nitrous oxide dimer: observation of combination bands of (14N2O)2 and (15N2O)2 involving the torsion and antigeared bending modes.

    PubMed

    Rezaei, M; Michaelian, K H; Moazzen-Ahmadi, N

    2012-03-28

    Spectra of the nonpolar nitrous oxide dimer in the region of the N(2)O ν(1) fundamental band were observed in a supersonic slit-jet apparatus. The expansion gas was probed using radiation from a quantum cascade or a tunable diode laser, with both lasers employed in a rapid-scan signal averaging mode. Four bands were observed and analyzed: new combination bands involving the intermolecular conrotation of the monomers (A(g) antigeared bend) for ((14)N(2)O)(2) and ((15)N(2)O)(2), the previously reported torsional combination band for ((14)N(2)O)(2) with improved signal-to-noise ratio, and the same torsional combination band for ((15)N(2)O)(2). The resulting frequencies for the intermolecular antigeared mode are 96.0926(1) and 95.4912(1) cm(-1) for ((14)N(2)O)(2) and ((15)N(2)O)(2), respectively. This is the third of the four intermolecular frequencies which has now been measured experimentally, the others being the out-of-plane torsion and the geared bend modes. Our experimental results are in good agreement with two recent high level ab initio theoretical calculations.

  12. Rate constant and thermochemistry for K + O2 + N2 = KO2 + N2.

    PubMed

    Sorvajärvi, Tapio; Viljanen, Jan; Toivonen, Juha; Marshall, Paul; Glarborg, Peter

    2015-04-09

    The addition reaction of potassium atoms with oxygen has been studied using the collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) method. KCl vapor was photolyzed with 266 nm pulses and the absorbance by K atoms at 766.5 nm was measured at various delay times with a narrow line width diode laser. Experiments were carried out with O2/N2 mixtures at a total pressure of 1 bar, over 748-1323 K. At the lower temperatures single exponential decays of [K] yielded the third-order rate constant for addition, kR1, whereas at higher temperatures equilibration was observed in the form of double exponential decays of [K], which yielded both kR1 and the equilibrium constant for KO2 formation. kR1 can be summarized as 1.07 × 10(-30)(T/1000 K)(-0.733) cm(6) molecule(-2) s(-1). Combination with literature values leads to a recommended kR1 of 5.5 × 10(-26)T(-1.55) exp(-10/T) cm(6) molecule(-2) s(-1) over 250-1320 K, with an error limit of a factor of 1.5. A van't Hoff analysis constrained to fit the computed ΔS298 yields a K-O2 bond dissociation enthalpy of 184.2 ± 4.0 kJ mol(-1) at 298 K and ΔfH298(KO2) = -95.2 ± 4.1 kJ mol(-1). The corresponding D0 is 181.5 ± 4.0 kJ mol(-1). This value compares well with a CCSD(T) extrapolation to the complete basis set limit, with all electrons correlated, of 177.9 kJ mol(-1).

  13. Vibrational Energy Coupling in Expanding N2/O2/NO Admixtures

    NASA Technical Reports Server (NTRS)

    Gilmore, John O.; Sharma, Surendra P.; Cavolowsky, John A. (Technical Monitor)

    1995-01-01

    Recent direct measurements of N2 and O2 vibrational populations in expansions of synthetic air show a closer coupling of the vibrational energies than indicated by adapting earlier experimental results from shock compressions to the nozzle expansion problem. An important difference between the shock wave and nozzle flow problems is the presence of NO in significant amounts throughout the relaxation in the case of a nozzle flow. This may account for the stronger coupling since NO is well suited to promote vibrational energy exchange. The results of a series of experiments and analysis examining vibrational energy coupling in expansions of admixtures approximating air are reported. N2 and O2 vibrational populations are determined by a single-pulse spontaneous Raman scattering technique. NO vibrational populations are determined by broadband absorption by the NO(y) system. The resulting data permit the role of NO in promoting vibrational energy coupling to be better understood, and are used to evaluate models of vibrational energy exchange for application to expanding flows.

  14. Electrical characterization of the flowing afterglow of N2 and N2/O2 microwave plasmas at reduced pressure

    NASA Astrophysics Data System (ADS)

    Afonso Ferreira, J.; Stafford, L.; Leonelli, R.; Ricard, A.

    2014-04-01

    A cylindrical Langmuir probe was used to analyze the spatial distribution of the number density of positive ions and electrons as well as the electron energy distribution function (EEDF) in the flowing afterglow of a 6 Torr N2 and N2/O2 plasma sustained by a propagating electromagnetic surface wave in the microwave regime. In pure N2 discharges, ion densities were in the mid 1014 m-3 in the pink afterglow and in the mid 1012 m-3 early in the late afterglow. In both pink and late afterglows, the ion population was much higher than the electron population, indicating non-macroscopically neutral media. The EEDF was close to a Maxwellian with an electron temperature of 0.5 ± 0.1 eV, except in the pink afterglow where the temperature rose to 1.1 ± 0.2 eV. This latter behavior is ascribed to N2 vibration-vibration pumping in the pink afterglow that increases the concentration of high N2 vibrational states and thus rises the electron temperature by vibration-electron collisions. After addition of small amounts of O2 in the nominally pure N2 discharge, the charged particles densities and average electron energy first strongly increased and then decreased with increasing O2 concentration. Based on these data and the evolution of the N2+(B) band emission intensities, it is concluded that a significant change in the positive ion composition of the flowing afterglow occurs, going from N2+ in nominally pure N2 discharges to NO+ after addition of trace amounts of O2 in N2.

  15. Comparison of Gas Temperatures Measured by Coherent Anti-Stokes Raman Spectroscopy (CARS) of O(2) and N(2).

    PubMed

    Reichardt, T A; Schrader, P E; Farrow, R L

    2001-02-20

    We investigate the accuracy of temperature measurements by coherent anti-Stokes Raman spectroscopy (CARS) of O(2) and use measurements taken with N(2) CARS and a thermocouple for comparison. Scanning vibrational CARS spectra of O(2) and N(2) were recorded over a broad range of temperatures: between 294 K and 1900 K in air that was heated in a tube furnace and at approximately 2450 K in a fuel-lean CH(4)-O(2)-N(2) flame. Temperatures were derived from least-squares fits of simulated and experimental spectra. Both the fundamental vibrational band and the first hot vibrational band were included in fitting. In the case of the tube furnace, the N(2) and the O(2) CARS temperature measurements agreed to within 3%, and results were similar with the thermocouple; in the flame the agreement was to within 1%. We conclude that, for cases in which O(2) is present in sufficient concentrations ( approximately 10% or greater), the accuracy of O(2) thermometry is comparable with that of N(2).

  16. The Effects of Flame Structure on Extinction of CH4-O2-N2 Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Du, J.; Axelbaum, R. L.; Gokoglu, S. (Technical Monitor)

    1996-01-01

    The effects of flame structure on the extinction limits of CH4-O2-N2 counterflow diffusion flames were investigated experimentally and numerically by varying the stoichiometric mixture fraction Z(sub st), Z(sub st) was varied by varying free-stream concentrations, while the adiabatic flame temperature T(sub ad) was held fixed by maintaining a fixed amount of nitrogen at the flame. Z(sub st) was varied between 0.055 (methane-air flame) and 0.78 (diluted- methane-oxygen flame). The experimental results yielded an extinction strain rate K(sub ext) of 375/s for the methane-air flame, increasing monotonically to 1042/s for the diluted-methane-oxygen flame. Numerical results with a 58-step Cl mechanism yielded 494/s and 1488/s, respectively. The increase in K(sub ext) with Z(sub st) for a fixed T(sub ad) is explained by the shift in the O2 profile toward the region of maximum temperature and the subsequent increase in rates for chain-branching reactions. The flame temperature at extinction reached a minimum at Z(sub st) = 0.65, where it was 200 C lower than that of the methane-air flame. This significant increase in resistance to extinction is seen to correspond to the condition in which the OH and O production zones are centered on the location of maximum temperature.

  17. Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

    NASA Technical Reports Server (NTRS)

    Estupinan, E. G.; Nicovich, J. M.; Li, J.; Cunnold, D. M.; Wine, P. H.

    2002-01-01

    Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and

  18. Estimates of N2 narcosis and O2 toxicity during submarine escapes from 600 to 1,000 fsw.

    PubMed

    Connor, Christopher W; Ferrigno, Massimo

    2009-01-01

    The U.S. Navy recommends submarine escape for depths down to 600 fsw, with deeper escapes entailing the risks of decompression sickness, nitrogen (N2) narcosis and CNS oxygen (O2) toxicity. However, the escape equipment, including the submarine escape and immersion equipment and the escape trunk, could probably function even at 1,000 fsw. Here we report a theoretical analysis of the risks of both N2 narcosis and CNS O2 toxicity for different escape profiles from 600 to 1,000 fsw. The effect of N2 narcosis, calculated as a function of N2 pressure in the brain using Gas Man software, was expressed as equivalent narcosis depth (END), corresponding to the depth at which the same pressure of N2 would be produced in the brain after five minutes of scuba diving with air. The risk of O2-induced convulsions was estimated using the model developed by Arieli et al. Different dwell times (DTs) at maximal pressure in the escape trunk (from 0 to 60 s) and lungs-to-brain circulation times (10 to 30 s) were included in our analysis. When DT in the escape trunk is very short (e.g., 10 s), the risk of either incapacitating N2 narcosis and/or O2-induced convulsions occurring in the trunk is low, even during escapes from 1,000 fsw.

  19. Ignition and Combustion of Pulverized Coal and Biomass under Different Oxy-fuel O2/N2 and O2/CO2 Environments

    NASA Astrophysics Data System (ADS)

    Khatami Firoozabadi, Seyed Reza

    This work studied the ignition and combustion of burning pulverized coals and biomasses particles under either conventional combustion in air or oxy-fuel combustion conditions. Oxy-fuel combustion is a 'clean-coal' process that takes place in O2/CO2 environments, which are achieved by removing nitrogen from the intake gases and recirculating large amounts of flue gases to the boiler. Removal of nitrogen from the combustion gases generates a high CO2-content, sequestration-ready gas at the boiler effluent. Flue gas recirculation moderates the high temperatures caused by the elevated oxygen partial pressure in the boiler. In this study, combustion of the fuels took place in a laboratory laminar-flow drop-tube furnace (DTF), electrically-heated to 1400 K, in environments containing various mole fractions of oxygen in either nitrogen or carbon-dioxide background gases. The experiments were conducted at two different gas conditions inside the furnace: (a) quiescent gas condition (i.e., no flow or inactive flow) and, (b) an active gas flow condition in both the injector and furnace. Eight coals from different ranks (anthracite, semi-snthracite, three bituminous, subbituminous and two lignites) and four biomasses from different sources were utilized in this work to study the ignition and combustion characteristics of solid fuels in O2/N2 or O2/CO2 environments. The main objective is to study the effect of replacing background N2 with CO2, increasing O2 mole fraction and fuel type and rank on a number of qualitative and quantitative parameters such as ignition/combustion mode, ignition temperature, ignition delay time, combustion temperatures, burnout times and envelope flame soot volume fractions. Regarding ignition, in the quiescent gas condition, bituminous and sub-bituminous coal particles experienced homogeneous ignition in both O2/N 2 and O2/CO2 atmospheres, while in the active gas flow condition, heterogeneous ignition was evident in O2/CO 2. Anthracite, semi

  20. Removal of NO in NO/N2, NO/N2/O2, NO/CH4/N2, and NO/CH4/O2/N2 systems by flowing microwave discharges.

    PubMed

    Hueso, José L; Gonzalez-Elipe, Agustín R; Cotrino, José; Caballero, Alfonso

    2007-02-15

    In this paper, continuing previous work, we report on experiments carried out to investigate the removal of NO from simulated flue gas in nonthermal plasmas. The plasma-induced decomposition of small concentrations of NO in N2 used as the carrier gas and O2 and CH4 as minority components has been studied in a surface wave discharge induced with a surfatron launcher. The reaction products and efficiency have been monitored by mass spectrometry as a function of the composition of the mixture. NO is effectively decomposed into N2 and O2 even in the presence of O2, provided always that enough CH4 is also present in the mixture. Other majority products of the plasma reactions under these conditions are NH3, CO, and H2. In the absence of O2, decomposition of NO also occurs, although in that case HCN accompanies the other reaction products as a majority component. The plasma for the different reaction mixtures has been characterized by optical emission spectroscopy. Intermediate excited species of NO*, C*, CN*, NH*, and CH* have been monitored depending on the gas mixture. The type of species detected and their evolution with the gas composition are in agreement with the reaction products detected in each case. The observations by mass spectrometry and optical emission spectroscopy are in agreement with the kinetic reaction models available in literature for simple plasma reactions in simple reaction mixtures.

  1. Fiber-Optic Determination of N2, O2, and Fuel Vapor in the Ullage of Liquid-Fuel Tanks

    NASA Technical Reports Server (NTRS)

    Nguyen, Quang-Viet

    2008-01-01

    A fiber-optic sensor system has been developed that can remotely measure the concentration of molecular oxygen (O2), nitrogen (N2), hydrocarbon vapor, and other gases (CO2, CO, H2O, chlorofluorocarbons, etc.) in the ullage of a liquid-fuel tank. The system provides an accurate and quantitative identification of the above gases with an accuracy of better than 1 percent by volume (for O2 or N2) in real-time (5 seconds). In an effort to prevent aircraft fuel tank fires or explosions similar to the tragic TWA Flight 800 explosion in 1996, OBIGGS are currently being developed for large commercial aircraft to prevent dangerous conditions from forming inside fuel tanks by providing an inerting gas blanket that is low in oxygen, thus preventing the ignition of the fuel/air mixture in the ullage. OBIGGS have been used in military aircraft for many years and are now standard equipment on some newer large commercial aircraft (such as the Boeing 787). Currently, OBIGGS are being developed for retrofitting to existing commercial aircraft fleets in response to pending mandates from the FAA. Most OBIGGS use an air separation module (ASM) that separates O2 from N2 to make nitrogen-enriched air from compressed air flow diverted from the engine (bleed air). Current OBIGGS systems do not have a closed-loop feedback control, in part, due to the lack of suitable process sensors that can reliably measure N2 or O2 and at the same time, do not constitute an inherent source of ignition. Thus, current OBIGGS operate with a high factor-of-safety dictated by process protocol to ensure adequate fuel-tank inerting. This approach is inherently inefficient as it consumes more engine bleed air than is necessary compared to a closed-loop controlled approach. The reduction of bleed air usage is important as it reduces fuel consumption, which translates to both increased flight range and lower operational costs. Numerous approaches to developing OBIGGS feedback-control sensors have been under

  2. Numerical simulations of turbulent premixed H2/O2/N2 flames with complex chemistry

    NASA Technical Reports Server (NTRS)

    Baum, M.; Poinsot, T. J.; Haworth, D. C.

    1992-01-01

    Premixed stoichiometric H2/O2/N2 flames propagating in two-dimensional turbulence were studied using direct numerical simulation (simulations in which all fluid and thermochemical scales are fully resolved) including realistic chemical kinetics and molecular transport. Results are compared with earlier zero-chemistry (flame sheet) and one-step chemistry simulations. Consistent with the simpler models, the turbulent flame with realistic chemistry aligns preferentially with extensive strain rates in the tangent plane and flame curvature probability density functions are close to symmetric with near-zero means. By contrast to simple-chemistry results with non-unity Lewis numbers (ratio of thermal to species diffusivity), local flame structure does not correlate with curvature but rather with tangential strain rate. Turbulent straining results in substantial thinning of the flame relative to the steady unstrained laminar case. Heat release and H2O2 contours remain thin and connected ('flamelet-like') while species including H-atom and OH are more diffuse. Peak OH concentration occurs well behind the peak heat-release zone. The feasibility of incorporating realistic chemistry into full turbulence simulations to address issues such as pollutant formation in hydrocarbon-air flames is suggested.

  3. Regional differences in the δO2/N2 records from East Antarctica over the last interglacial

    NASA Astrophysics Data System (ADS)

    Bazin, L.; Landais, A.; Masson-Delmotte, V.; Kageyama, M.; Paillard, D.; Bopp, L.; Ritz, C.; Leuenberger, M.

    2013-12-01

    Ice cores are the only climate archives offering samples of past atmosphere. The air is trapped at around 100 m under the surface, where the snow is compacted into ice. During this process, multiple influences may modify the air composition as the quantity of insolation received at the surface impacts snow metamorphism and hence air trapping conditions at the basis of the firn (top ~100m of the ice sheet). Analyses of trapped air in ice cores thus give us information on both local and global scales. In this study, we focus on temporal variations of elemental and isotopic composition of oxygen from East Antarctic ice cores. On the one hand, the δ18Oatm, uniformly distributed in the atmosphere, is known to be related to the hydrological cycle and the vegetation cover (Landais et al., 2010), and can be linked to the precession variations. The δO2/N2, on the other hand, appears to be influenced by the local insolation, probably because of modification of the snow structure affecting pore close-off. These two quantities have largely been used as orbital tuning tools for dating purposes in several ice cores from Antarctica (Bender 2002, Suwa et Bender 2008, Kawamura et al., 2007, Dreyfus et al., 2007,Landais et al., 2012, Bazin et al., 2013). Still, gaps in our understanding of the exact mechanisms explaining the δ18Oatm and δO2/N2 variations lead to quite large uncertainties when using these proxies as tie-points for dating purposes. In this study, we use several ice core records in low accumulation rate sites of East Antarctica to decipher global and local effects on the δO2/N2 records. First, we present a compilation of δO2/N2 measurements of the Dome F, Vostok and Dome C ice cores over the last interglacial period. While Dome F and Vostok data were corrected for gas loss during several years of storage at -25°C, new measurements of the air isotopic composition on the Dome C ice core were performed on well-conserved ice (-50°C). Different δO2/N2 mean levels

  4. Probe Decomposition of Methylammonium Lead Iodide Perovskite in N2 and O2 by in Situ Infrared Spectroscopy.

    PubMed

    Yu, Xiaozhou; Qin, Ying; Peng, Qing

    2017-02-16

    Packaging methylammonium lead iodide perovskite (MAPbI3)-based solar cells with N2 or dry air is a promising solution for its application in outdoor photovoltaics. However, the effect of N2 and O2 on the decomposition chemistry and kinetics of MAPbI3 is not yet well-understood. With in situ Fourier transform infrared spectroscopy measurements, we show that the effective activation energy for the degradation of MAPbI3 in N2 is ∼120 kJ/mol. The decomposition of MAPbI3 is greatly accelerated by exposure to O2 in the dark. As a result of the synergistic effect between O2 and a HeNe laser (633 nm), the degradation rate is further increased with photon flux. This synergistic effect reduces the effective activation energy of degradation of MAPbI3 to ∼50 kJ/mol. The solid decomposition products after annealing in N2 and O2 at 150 °C or below do not have absorbance between 650 and 4000 cm(-1).

  5. Method for measuring changes in the atmospheric O2/N2 ratio by a gas chromatograph equipped with a thermal conductivity detector

    NASA Astrophysics Data System (ADS)

    Tohjima, Yasunori

    2000-06-01

    We present a method for measuring changes in the atmospheric O2/N2 ratio based on data from a gas chromatograph (GC) equipped with a thermal conductivity detector (TCD). In this method, O2 and N2 in an air sample are separated on a column filled with molecular sieve 5A with H2 carrier gas. Since the separated O2 includes Ar, which has a retention time similar to that of O2, the (O2+Ar)/N2 ratio is actually measured. The change in the measured (O2+Ar)/N2 ratio can be easily converted to that in the O2/N2 ratio with a very small error based on the fact that the atmospheric Ar/N2 ratio is almost constant. The improvements to achieve the high-precision measurement include stabilization of the pressure at the GC column head and at the outlets of the TCD and the sample loop. Additionally, the precision is improved statistically by repeating alternate analyses of sample and a reference gas. The standard deviation of the replicate cycles of reference and sample analyses is about 18 per meg (corresponding to 3.8 parts per million (ppm) O2 in air). This means that the standard error is about 7 per meg (1.5 ppm O2 in air) for seven cycles of alternate analyses, which takes about 70 min. The response of this method is likely to have a 2% nonlinearity. Ambient air samples are collected under pressure in glass flasks equipped with two stopcocks sealed by Viton O-rings at both ends. Pressure depletion in the flask during the O2/N2 measurement does not cause any detectable change in the O2/N2 ratio, but the O2/N2 ratio in the flask was found to gradually decrease during the storage period. We also present preliminary results from air samples collected at Hateruma Island (latitude 24°03'N, longitude 123°49') from July 1997 through March 1999. The observed O2/N2 ratios clearly show a seasonal variation, increasing in spring and summer and decreasing in autumn and winter.

  6. Ozone production and losses in N2/O2 mixtures in an ozone generator

    NASA Astrophysics Data System (ADS)

    Mankelevich, Yu. A.; Poroykov, A. Yu.; Rakhimova, T. V.; Voloshin, D. G.; Chukalovskii, A. A.; Zosimov, A. V.; Lunin, V. V.; Samoilovich, V. G.

    2016-09-01

    Nonunique ozone concentrations at the output of an ozone generator under identical external conditions of barrier discharge activation of N2/O2 mixtures but with different prehistories of operating practice and employed gas mixtures are investigated theoretically. An analytical approach is developed to determine the ozone yield with regard for its heterogeneous loss. Plasma-chemical and electron kinetics in the N2/O2-mixtures are calculated numerically. The results of numerical calculations are compared to experimental data obtained by the authors. It is noted that the heterogeneous loss of ozone is the probable reason for the observed variety of behavior of O3 concentrations, depending on prehistory of ozone generator operation, along with the N2 and O2 gas flow rates and the specific active power.

  7. O2 and N2O activation by Bi-, Tri-, and tetranuclear Cu clusters in biology.

    PubMed

    Solomon, Edward I; Sarangi, Ritimukta; Woertink, Julia S; Augustine, Anthony J; Yoon, Jungjoo; Ghosh, Somdatta

    2007-07-01

    Copper-cluster sites in biology exhibit unique spectroscopic features reflecting exchange coupling between oxidized Cu's and e (-) delocalization in mixed valent sites. These novel electronic structures play critical roles in O 2 binding and activation for electrophilic aromatic attack and H-atom abstraction, the 4e (-)/4H (+) reduction of O 2 to H 2O, and in the 2e (-)/2H (+) reduction of N 2O. These electronic structure/reactivity correlations are summarized below.

  8. Wavelength-dependent UV photodesorption of pure N2 and O2 ices

    NASA Astrophysics Data System (ADS)

    Fayolle, E. C.; Bertin, M.; Romanzin, C.; Poderoso, H. A. M.; Philippe, L.; Michaut, X.; Jeseck, P.; Linnartz, H.; Öberg, K. I.; Fillion, J.-H.

    2013-08-01

    Context. Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. Aims: N2 and O2 are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Methods: Tunable radiation from the DESIRS beamline at the SOLEIL synchrotron in the astrophysically relevant 7 to 13.6 eV range is used to irradiate pure N2 and O2 thin ice films. Photodesorption of molecules is monitored through quadrupole mass spectrometry. Absolute rates are calculated by using the well-calibrated CO photodesorption rates. Strategic N2 and O2 isotopolog mixtures are used to investigate the importance of dissociation upon irradiation. Results: N2 photodesorption mainly occurs through excitation of the b1Πu state and subsequent desorption of surface molecules. The observed vibronic structure in the N2 photodesorption spectrum, together with the absence of N3 formation, supports that the photodesorption mechanism of N2 is similar to CO, i.e., an indirect DIET (Desorption Induced by Electronic Transition) process without dissociation of the desorbing molecule. In contrast, O2 photodesorption in the 7-13.6 eV range occurs through dissociation and presents no vibrational structure. Conclusions: Photodesorption rates of N2 and O2 integrated over the far-UV field from various star-forming environments are lower than for CO. Rates vary between 10-3 and 10-2 photodesorbed molecules per incoming photon.

  9. Vibrational relaxation in expanding N2 and air

    NASA Technical Reports Server (NTRS)

    Sebacher, D. I.; Guy, R. W.

    1974-01-01

    New N2 vibrational temperature data, obtained in expanding N2 and air using the electron beam technique, are analyzed permitting the vibrational relaxation times to be determined as a function of temperature. In addition, the effects on N2 vibrational relaxation times of direct vibrational energy transfer between N2 and H2O, between N2 and O2, and between N2 and free electrons introduced from arc contaminants are analyzed. The vibrational relaxation times determined from the present measurements agree with those measured in the expanding flows of shock tunnels and impact tubes. These expanding data also agree with relaxation times observed in acoustical resonant cavities where alternating compressions and expansions take place. The relaxation times in expanding flows (vib-tran exchange process) are found to be approximately 50 times faster than those measured in the compressing flow of shock tubes (tran-vib exchange process). This evidence strongly supports the concept that one relaxation time distribution cannot be applied to both exchange processes.

  10. Turbulence in Supercritical O2/H2 and C7H16/N2 Mixing Layers

    NASA Technical Reports Server (NTRS)

    Bellan, Josette; Harstad, Kenneth; Okong'o, Nora

    2003-01-01

    This report presents a study of numerical simulations of mixing layers developing between opposing flows of paired fluids under supercritical conditions, the purpose of the study being to elucidate chemical-species-specific aspects of turbulence. The simulations were performed for two different fluid pairs O2/H2 and C7H16/N2 at similar reduced initial pressures (reduced pressure is defined as pressure divided by critical pressure). Thermodynamically, O2/H2 behaves more nearly like an ideal mixture and has greater solubility, relative to C7H16/N2, which departs strongly from ideality. Because of a specified smaller initial density stratification, the C7H16/N2 layers exhibited greater levels of growth, global molecular mixing, and turbulence. However, smaller density gradients at the transitional state for the O2/H2 system were interpreted as indicating that locally, this system exhibits enhanced mixing as a consequence of its greater solubility and closer approach to ideality. These thermodynamic features were shown to affect entropy dissipation, which was found to be larger for O2/H2 and concentrated in high-density-gradient-magnitude regions that are distortions of the initial density-stratification boundary. In C7H16/N2, the regions of largest dissipation were found to lie in high-density-gradient-magnitude regions that result from mixing of the two fluids.

  11. Generating Breathable Air Through Dissociation of N2O

    NASA Technical Reports Server (NTRS)

    Zubrin, Robert; Frankie, Brian

    2006-01-01

    A nitrous oxide-based oxygen-supply system (NOBOSS) is an apparatus in which a breathable mixture comprising 2/3 volume parts of N2 and 1/3 volume part of O2 is generated through dissociation of N2O. The NOBOSS concept can be adapted to a variety of applications in which there are requirements for relatively compact, lightweight systems to supply breathable air. These could include air-supply systems for firefighters, divers, astronauts, and workers who must be protected against biological and chemical hazards. A NOBOSS stands in contrast to compressed-gas and cryogenic air-supply systems. Compressed-gas systems necessarily include massive tanks that can hold only relatively small amounts of gases. Alternatively, gases can be stored compactly in greater quantities and at low pressures when they are liquefied, but then cryogenic equipment is needed to maintain them in liquid form. Overcoming the disadvantages of both compressed-gas and cryogenic systems, the NOBOSS exploits the fact that N2O can be stored in liquid form at room temperature and moderate pressure. The mass of N2O that can be stored in a tank of a given mass is about 20 times the mass of compressed air that can be stored in a tank of equal mass. In a NOBOSS, N2O is exothermically dissociated to N2 and O2 in a main catalytic reactor. In order to ensure the dissociation of N2O to the maximum possible extent, the temperature of the reactor must be kept above 400 C. At the same time, to minimize concentrations of nitrogen oxides (which are toxic), it is necessary to keep the reactor temperature at or below 540 C. To keep the temperature within the required range throughout the reactor and, in particular, to prevent the formation of hot spots that would be generated by local concentrations of the exothermic dissociation reaction, the N2O is introduced into the reactor through an injector tube that features carefully spaced holes to distribute the input flow of N2O widely throughout the reactor. A NOBOSS

  12. Production of NO, N2O and N2 by extracted soil bacteria, regulation by NO2(-) and O2 concentrations.

    PubMed

    Morley, Nicholas; Baggs, Elizabeth M; Dörsch, Peter; Bakken, Lars

    2008-07-01

    The oxygen control of denitrification and its emission of NO/N2O/N2 was investigated by incubation of Nycodenz-extracted soil bacteria in an incubation robot which monitors O2, NO, N2O and N2 concentrations (in He+O2 atmosphere). Two consecutive incubations were undertaken to determine (1) the regulation of denitrification by O2 and NO2(-) during respiratory O2 depletion and (2) the effects of re-exposure to O2 of cultures with fully expressed denitrification proteome. Early denitrification was only detected (as NO and N2O) at O2 in treatments with NO2(-), and the rates were three orders of magnitude lower than the rates observed after oxygen depletion (with N2 as the primary product). When re-exposed to O2, the cultures continued to denitrify (8-55% of the rates during the foregoing anoxic phase), but its main product was N2O. The N2O reductase activity recovered as oxygen was being depleted. The results suggest that expression of the denitrifying proteome may result in significant subsequent aerobic denitrification, and this has profound implications for the understanding and modelling of denitrification and N2O emission. Short anoxic spells caused by transient flooding during rainfall, could lead to subsequent unbalanced aerobic denitrification, in which N2O is a major end product.

  13. Environmental conditions affecting concentrations of He, CO2, O2 and N2 in soil gases

    USGS Publications Warehouse

    Hinkle, Margaret E.

    1994-01-01

    The measurement of concentrations of volatile species in soil gases has potential for use in geochemical exploration for concealed ore deposits and for monitoring of subsurface contaminants. However, the interpretation of anomalies in surficial gases can be difficult because soil-gas concentrations are dependent on both meteorological and environmental conditions.For this study, concentrations of He, CO2, O2 and N2 and meteorological conditions were monitored for 10–14 months at eight nonmineralized sites in both humid and dry environments. Gases were collected at 0.6–0.7-m depth at seven sites. At one site, gases were collected from 0.3-, 0.6-, 1.2-, and 2.0-m depths; diurnal monitoring studies were conducted at this site also. Rain and snowfall, soil and air temperatures, barometric pressure, and relative humidity were monitored at all the sites. The sand, silt and clay content, and the organic carbon content of surficial soil were measured at each site.Meteorological conditions generally affected He and CO2 concentrations in the same way at all the sites; however, these effects were modified by local environmental conditions. Both seasonal and diurnal concentration changes occurred. The most important seasonal concentration changes were related to rain and snowfall and soil and air temperatures. Seasonal changes tended to be larger then the diurnal changes, but both could be related to the same processes. Local conditions of soil type and organic content affected the amount of pore space and moisture present in the soil and therefore the soil-gas concentrations.

  14. Absolute intensity and polarization of rotational Raman scattering from N2, O2, and CO2

    NASA Technical Reports Server (NTRS)

    Penney, C. M.; St.peters, R. L.; Lapp, M.

    1973-01-01

    An experimental examination of the absolute intensity, polarization, and relative line intensities of rotational Raman scattering (RRS) from N2, O2, and CO2 is reported. The absolute scattering intensity for N2 is characterized by its differential cross section for backscattering of incident light at 647.1 nm, which is calculated from basic measured values. The ratio of the corresponding cross section for O2 to that for N2 is 2.50 plus or minus 5 percent. The intensity recent for N2, O2, and CO2 are shown to compare favorably to values calculated from recent measurements of the depolarization of Rayleigh scattering plus RRS. Measured depolarizations of various RRS lines agree to within a few percent with the theoretical value of 3/4. Detailed error analyses are presented for intensity and depolarization measurements. Finally, extensive RRS spectra at nominal gas temperatures of 23 C, 75 C, and 125 C are presented and shown to compare favorably to theoretical predictions.

  15. State-selected ion-molecule reactions: The charge-transfer N2+(X,v+)+O2O2++N2

    NASA Astrophysics Data System (ADS)

    Knott, W. J.; Proch, D.; Kompa, K. L.

    1999-05-01

    The charge-transfer process, which is the subject of this paper, is an important link in the chain of reactive events which occur in the E- and F-regions of the earth's atmosphere. The reaction is suspected to proceed via the formation of a short-lived intermediate complex (N2O2)+. The transient existence of this van der Waals molecule has been inferred from molecular orbital and ab initio arguments. To the present day, however, none of the numerous studies focusing on this system has provided proof of its existence. The positive evidence obtained from this experiment is of an indirect nature, based on measurements of the kinetic energy of the released O2+ as a function of the expendable center-of-mass collision energy. The results point to an indirect reaction (i.e., via an intermediate) in the low energy regime, and a direct process once the center-of-mass energy exceeds the bond energy of the complex. A model description which contracts both pictures matches the complete set of energy-dependent cross section data in a very persuasive manner. A competing reactive channel which has also been given attention results in the formation of NO+. The initiation of this reaction requires a cleavage of the N-N bond, which should be eased by vibrational excitation of the reagent ion. The cross section data, however, turn out to be unaffected by such details of reagent state preparation.

  16. [The nitrate- and nitrite-dependent O2-evolution in N 2 by Ankistrodesmus braunii].

    PubMed

    Ullrich, W R

    1974-06-01

    O2-evolution in N2 by young cells of synchronous Ankistrodesmus braunii was measured manometrically in the presence and in the absence of nitrate or nitrite. Nitrate-starved cells produce O2 as a function of nitrate concentration with an optimum at 10 mM nitrate. The optimum rates are strongly dependent upon the pH of the medium culminating at pH 8.0.Nitrite excretion is initially slow and has its optimum at the same nitrate concentration as O2-evolution. It is slower under anaerobic conditions than in the presence of CO2 and slower at pH 5.6 than at pH 8.0. At pH 8.0 in N2 an accumulation of nitrite starts 40 to 100 min after the addition of nitrate to the algae.O2-evolution is faster with nitrite than with nitrate. No optimum curve is observed at pH 8.0 with various concentrations of nitrite in the medium; however, at pH 5.6 a distinct peak is found at 3 mM nitrite. This peak is found for a fast short-time reaction as well as for the following low rates of O2-evolution.The uncoupler carbonylcyanide-m-chlorophenylhydrazone (CCCP) equally inhibits nitrate- and nitrite-dependent O2-evolution and the incorporation of (32)P into cellular phosphate compounds. There is no indication of uncoupling in vivo of nitrite reduction which is completely independent of ATP in vitro. The inhibition of the nitrate-dependent O2-evolution by high concentrations of nitrate cannot be explained by an accumulation of products such as ammonia or nitrite.

  17. N 2- and O 2-broadening coefficients of C 2H 2 IR lines

    NASA Astrophysics Data System (ADS)

    Bouanich, J. P.; Lambot, D.; Blanquet, G.; Walrand, J.

    1990-04-01

    Pressure-broadening parameters of six lines belonging to the ν5 band of C 2H 2 in collision with N 2 have been measured with a tunable diode-laser spectrometer in order to complete up to J = 33 our earlier measurements (D. Lambot, G. Blanquet, and J. P. Bouanich, J. Mol. Spectrosc.136, 86-92 (1989)) on the broadening of C 2H 2 by N 2 and O 2 at 297 K. These N 2- and O 2-broadening coefficients have been first calculated on the basis of the Anderson-Tsao-Curnutte theory; in this approach, we show that the short-range interactions which contribute significantly to the linewidths are not correctly treated. Next, we consider the improved semiclassical model proposed by Robert and Bonamy. The intermolecular potential consists in the addition of the atom-atom interaction model to the quadrupolar interactions. The limited radial spherical harmonics expansion of the atom-atom potential, from which expressions for the differential cross section were derived, appears to be quite insufficient at short intermolecular distances. Therefore, we use a more accurate representation of this potential, avoiding an inadequate truncation and keeping the analytic expressions obtained by Bonamy and Robert. In the calculations we take into account the contributions derived from the radial functions U000( r), U200( r), and U220( r), as well as from U400( r). A theoretical expression is obtained for the U400 contribution to the differential cross section. The results of the calculations arising from the exact radial expansion of the atom-atom potential appear to be significantly larger for high J lines than those arising from the truncated expansion. The latter results, which do not include adjustable atom-atom parameters, are in good agreement with experimental broadening coefficients for C 2H 2O 2 and in reasonable agreement (except at large J values) for C 2H 2N 2. It is also shown that the contributions to the linewidths derived from U400 are rather small for C 2H 2N 2 and more

  18. Helicity in Supercritical O2/H2 and C7H16/N2 Mixing Layers

    NASA Technical Reports Server (NTRS)

    Okongo, Nora; Bellan, Josette

    2004-01-01

    This report describes a study of databases produced by direct numerical simulation of mixing layers developing between opposing flows of two fluids under supercritical conditions, the purpose of the study being to elucidate chemical-species-specific aspects of turbulence, with emphasis on helicity. The simulations were performed for two different fluid pairs -- O2/H2 and C7H16/N2 -- at similar values of reduced pressure.

  19. Annual mean mixing ratios of N2, Ar, O2, and CO in the martian atmosphere

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, Vladimir A.

    2017-09-01

    The precise mixing ratios of N2, Ar, O2, and CO measured by the MSL Curiosity quadrupole mass spectrometer must be corrected for the seasonal variations of the atmospheric pressure to reproduce annual mean mixing ratios on Mars. The corrections are made using measurements for the first year of the Viking Landers 1 and 2 and the Mars Climate Database data. The mean correction factor is 0.899 ± 0.006 resulting in annual mean mixing ratios of (1.83 ± 0.03)% for N2, (1.86 ± 0.02)% for Ar, (1.56 ± 0.06) × 10-3 for O2, and 673 ± 2.6 ppm for CO. The O2 mixing ratio agrees with the Herschel value within its uncertainty, the ground-based observations corrected for the dust extinction, and photochemical models by Nair et al. (1994) and Krasnopolsky (2010). The CO mixing ratio is in excellent agreement with the MRO/CRISM value of 700 ppm and with 667, 693, and 684 ppm recently observed at LS = 60, 89, and 110° and corrected to the annual mean conditions. Lifetimes of N2 and Ar are very long in the martian atmosphere, and differences between the MSL and Viking data on these species cannot be attributed to their variations.

  20. Proton transfer reactions from H3/+/ ions to N2, O2, and CO molecules

    NASA Technical Reports Server (NTRS)

    Kim, J. K.; Theard, L. P.; Huntress, W. T., Jr.

    1975-01-01

    The rate constants for proton transfer from H3(+) ions to N2, O2, and CO have been measured as function of hydrogen-buffer-gas partial pressure. The rate constant for proton transfer from H3(+) to N2 shows a very large pressure dependence, increasing from 1.0 by 10 to the -9th power cu cm/s at low H2 partial pressures to 1.7 by 10 to the -9th power cu cm/s at high H2 partial pressures. The rate constants for proton transfer from H3(+) to O2 and CO are constant with partial pressure of H2. The roles of excess vibrational energy in H3(+) ions and of equilibrium between forward and back reactions are discussed. Back reaction is observed only for the reaction of H3(+) ions with O2, and an equilibrium constant of 2.0 (plus or minus 0.4) at 298 K has been determined. From these data, the proton affinity of O2 is deduced to be 0.47 (plus or minus 0.11) kcal/mole higher than that of H2.

  1. Vibrational frequency shifts of H2, N2 and O2 adsorbed in NaA zeolite.

    NASA Astrophysics Data System (ADS)

    Koubi, Laure; Blain, Monique; Cohen De Lara, Evelyne; Leclercq, Jean-Marie

    1995-04-01

    We report ab initio calculations on H2,N2 and O2 and on the same molecules in interaction with a Na+ cation. The results are compared to experimental data on induced infrared band of H2, N2 and O2 adsorbed in NaA zeolite. (AIP)

  2. Fast gas heating in N2/O2 mixtures under nanosecond surface dielectric barrier discharge: the effects of gas pressure and composition

    PubMed Central

    Nudnova, M. M; Kindysheva, S. V; Aleksandrov, N. L; Starikovskii, A. Yu

    2015-01-01

    The fractional electron power quickly transferred to heat in non-equilibrium plasmas was studied experimentally and theoretically in N2/O2 mixtures subjected to high electric fields. Measurements were performed in and after a nanosecond surface dielectric barrier discharge at various (300–750 Torr) gas pressures and (50–100%) N2 percentages. Observations showed that the efficiency of fast gas heating is almost independent of pressure and becomes more profound when the fraction of O2 in N2/O2 mixtures increases. The processes that contribute towards the fast transfer of electron energy to thermal energy were numerically simulated under the conditions considered. Calculations were compared with measurements and the main channels of fast gas heating were analysed at the gas pressures, compositions and electric fields under study. It was shown that efficient fast gas heating in the mixtures with high fraction of O2 is due to a notable contribution of heat release during quenching of electronically excited N2 states in collisions with O2 molecules and to ion–ion recombination. The effect of hydrocarbon addition to air on fast gas heating was numerically estimated. It was concluded that the fractional electron power transferred to heat in air, as a first approximation, could be used to estimate this effect in lean and stoichiometric hydrocarbon–air mixtures. PMID:26170431

  3. Enhanced O-2 Selectivity versus N-2 by Partial Metal Substitution in Cu-BTC

    SciTech Connect

    Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.; Zhang, Xiaoyi; Nenoff, Tina M.

    2015-03-24

    Here, we describe the homogeneous substitution of Mn, Fe, and Co at various levels into a prototypical metal organic framework (MOP), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O-2/N-2 selectivities determined experimentally at 77 K and the difference in O-2 and N-2 binding energies calculated from DFT modeling data: Mn > Fe Co >> Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273-298 K) as compared to all other metals studied, indicative of favorable interactions between N-2 and coordinatively unsaturated Fe metal centers. Interestingly, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.

  4. Enhanced O2 selectivity versus N2 by partial metal substitution in Cu-BTC

    DOE PAGES

    Sava Gallis, Dorina F.; Parkes, Marie V.; Greathouse, Jeffery A.; ...

    2015-03-05

    Here we describe the homogeneous substitution of Mn, Fe and Co at various levels into a prototypical metal-organic framework (MOF), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O2/N2 selectivities determined experimentally at 77 K and the difference in O2 and N2 binding energies calculated from DFT modelingmore » data: Mn > Fe > Co > Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273 K - 298 K) as compared to all other metals studied, indicative of favorable interactions between N2 and coordinatively unsaturated Fe metal centers. Furthermore, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.« less

  5. Turbulent piloted partially-premixed flames with varying levels of O2/N2: stability limits and PDF calculations

    NASA Astrophysics Data System (ADS)

    Juddoo, Mrinal; Masri, Assaad R.; Pope, Stephen B.

    2011-12-01

    This paper reports measured stability limits and PDF calculations of piloted, turbulent flames of compressed natural gas (CNG) partially-premixed with either pure oxygen, or with varying levels of O2/N2. Stability limits are presented for flames of CNG fuel premixed with up to 20% oxygen as well as CNG-O2-N2 fuel where the O2 content is varied from 8 to 22% by volume. Calculations are presented for (i) Sydney flame B [Masri et al. 1988] which uses pure CNG as well as flames B15 to B25 where the CNG is partially-premixed with 15-25% oxygen by volume, respectively and (ii) Sandia methane-air (1:3 by volume) flame E [Barlow et al. 2005] as well as new flames E15 and E25 that are partially-premixed with 'reconstituted air' where the O2 content in nitrogen is 15 and 25% by volume, respectively. The calculations solve a transported PDF of composition using a particle-based Monte Carlo method and employ the EMST mixing model as well as detailed chemical kinetics. The addition of oxygen to the fuel increases stability, shortens the flames, broadens the reaction zone, and shifts the stoichiometric mixture fraction towards the inner side of the jet. It is found that for pure CNG flames where the reaction zone is narrow (∼0.1 in mixture fraction space), the PDF calculations fail to reproduce the correct level of local extinction on approach to blow-off. A broadening in the reaction zone up to about 0.25 in mixture fraction space is needed for the PDF/EMST approach to be able to capture these finite-rate chemistry effects. It is also found that for the same level of partial premixing, increasing the O2/N2 ratio increases the maximum levels of CO and NO but shifts the peak to richer mixture fractions. Over the range of oxygenation investigated here, stability limits have shown to improve almost linearly with increasing oxygen levels in the fuel and with increasing the contribution of release rate from the pilot.

  6. Efficient vibrational Raman conversion in O2 and N2 cells by use of superfluorescence seeding

    NASA Technical Reports Server (NTRS)

    Zhang, Barry; Lempert, Walter R.; Miles, R. B.; Diskin, Glenn

    1993-01-01

    We report first-Stokes vibrational conversion efficiency of 21 percent and 35 percent, respectively, in high-pressure O2- and N2-stimulated Raman cells. Broadband superfluorescence is employed to seed these Raman cells, significantly increasing the conversion efficiences with no measured effect on the Raman spectrum. The addition of helium buffer gas reduces competition from stimulated Brillouin scattering and improves the pulse-to-pulse stability and spatial mode quality by increasing the thermal conductivity. Further improvement of the spatial mode quality is achieved by use of gentle heating on the bottom of the cell to induce convection.

  7. Efficient vibrational Raman conversion in O2 and N2 cells by use of superfluorescence seeding

    NASA Technical Reports Server (NTRS)

    Zhang, Barry; Lempert, Walter R.; Miles, R. B.; Diskin, Glenn

    1993-01-01

    We report first-Stokes vibrational conversion efficiency of 21 percent and 35 percent, respectively, in high-pressure O2- and N2-stimulated Raman cells. Broadband superfluorescence is employed to seed these Raman cells, significantly increasing the conversion efficiences with no measured effect on the Raman spectrum. The addition of helium buffer gas reduces competition from stimulated Brillouin scattering and improves the pulse-to-pulse stability and spatial mode quality by increasing the thermal conductivity. Further improvement of the spatial mode quality is achieved by use of gentle heating on the bottom of the cell to induce convection.

  8. Observation of mixed acetylene - Nitrous oxide trimers: Infrared spectra of C2H2-(N2O)2 and (C2H2)2-N2O

    NASA Astrophysics Data System (ADS)

    Sheybani-Deloui, S.; Yousefi, M.; Norooz Oliaee, J.; McKellar, A. R. W.; Moazzen-Ahmadi, N.

    2014-12-01

    Infrared spectra of the lowest energy isomers of C2H2-(N2O)2 and (C2H2)2-N2O were observed in the region of the ν1 fundamental band of the N2O monomer (∼2224 cm-1) using a tunable diode laser and/or a CW quantum cascade laser to probe a pulsed supersonic slit jet expansion. One infrared band was measured for each trimer. The band for C2H2-(N2O)2 corresponds to the out-of-phase vibrations of the pair of equivalent N2O monomers. It is blue shifted by about 10 cm-1 with respect to the free N2O monomer. The band for (C2H2)2-N2O is slightly less blue shifted (centered at 2232.81 cm-1). It can be simulated as a predominately a-type band. In addition to the normal isotopologues, the corresponding bands for C2D2-(N2O)2 and (C2D2)2-N2O were also observed. The structures of these trimers are similar to those of the lowest energy isomers of the analogous OCS - acetylene trimers reported previously, that is, a twisted barrel with C2 symmetry for C2H2-(N2O)2 and a distorted T-shaped acetylene dimer with a coplanar N2O beside the stem of the T for (C2H2)2-N2O. Here, we present our observation and experimental results, which agree well with calculations based on distributed multipole pair potentials.

  9. New metallicity calibration for Seyfert 2 galaxies based on the N2O2 index

    NASA Astrophysics Data System (ADS)

    Castro, C. S.; Dors, O. L.; Cardaci, M. V.; Hägele, G. F.

    2017-01-01

    We derive a new relation between the metallicity of Seyfert 2 Active Galactic Nuclei (AGNs) and the intensity of the narrow emission-lines ratio N2O2=log([N II]λ6584/[O II]λ3727). The calibration of this relation was performed determining the metallicity (Z) of a sample of 58 AGNs through a diagram containing the observational data and the results of a grid of photoionization models obtained with the CLOUDY code. We find the new Z/Z⊙-N2O2 relation using the obtained metallicity values and the corresponding observational emission line intensities for each object of the sample. Estimations derived through the use of this new calibration indicate that narrow line regions of Seyfert 2 galaxies exhibit a large range of metallicities (0.3 ≲ Z/Z_{⊙} ≲ 2.0), with a median value Z ≈ Z⊙. Regarding the possible existence of correlations between the luminosity L(Hβ), the electron density, and the color excess E(B-V) with the metallicity in this kind of objects, we do not find correlations between them.

  10. New metallicity calibration for Seyfert 2 galaxies based on the N2O2 index

    NASA Astrophysics Data System (ADS)

    Castro, C. S.; Dors, O. L.; Cardaci, M. V.; Hägele, G. F.

    2017-05-01

    We derive a new relation between the metallicity of Seyfert 2 active galactic nuclei (AGNs) and the intensity of the narrow emission-lines ratio N2O2 = log([N ii] λ6584/[O ii] λ3727). The calibration of this relation was performed by determining the metallicity (Z) of a sample of 58 AGNs through a diagram containing the observational data and the results of a grid of photoionization models obtained with the cloudy code. We find the new Z/Z⊙-N2O2 relation using the obtained metallicity values and the corresponding observational emission-line intensities for each object of the sample. Estimations derived through the use of this new calibration indicate that the narrow-line regions of Seyfert 2 galaxies exhibit a large range of metallicities (0.3 ≲ Z/Z⊙ ≲ 2.0), with a median value Z ≈ Z⊙. Regarding the possible existence of correlations between the luminosity L(Hβ), the electron density and the colour excess E(B - V) with the metallicity in this kind of objects, we do not find correlations between them.

  11. Effect of N2O ratio on the crystallization temperature of ZrO2 film deposited on Si by reactive sputtering in Ar/O2/N2O plasma

    NASA Astrophysics Data System (ADS)

    Faruque, Sk Abdul Kader Md; Prasad Giri, Rajendra; Chakraborty, Supratic

    2016-11-01

    The effect of nitrous oxide ratios in the Ar/ O2/ N2O plasma on the ZrO2 films deposited on Si using dc magnetron reactive system is studied by differential scanning calorimetry (DSC) where the Ar:O2 ratio is fixed at 4:1. Further, grazing angle x-ray reflectivity (GIXRR), grazing angle x-ray diffraction (GIXRD) and atomic force microscopy (AFM) techniques are also employed to characterize the films. The DSC study shows an anomalous variation of the glass temperature when the N2O ratio in the Ar/O2/N2O plasma changes from 0.25 to 2 with respect to the control ZrO2 sample deposited without N2O. An increase in glass temperature by ∼70 °C is observed for the N2O ratio at 1. A further rise in N2O ratio results in the reduction of the glass temperature. The GIXRR study indicates that the thickness of the samples decreases with the increase in N2O ratios beyond 0.8. Further, increasing N2O ratio results in an increase in surface and interface roughness for the as-deposited samples. But both the roughnesses decrease upon annealing the samples above their respective crystallization temperatures. The AFM results also corroborates the observation. Moreover, the GIXRD study indicates the formation of Γ-Zr2ON2 along with the monoclinic and tetragonal ZrO2 at the highest ratio of N2O in the Ar:O2:N2O plasma.

  12. N2-, O2- and He-collision-induced broadening of sulfur dioxide ro-vibrational lines in the 9.2 μm atmospheric window

    NASA Astrophysics Data System (ADS)

    Tasinato, Nicola; Pietropolli Charmet, Andrea; Stoppa, Paolo; Giorgianni, Santi; Buffa, Giovanni

    2014-01-01

    Sulfur dioxide (SO2) is a molecule of considerable interest for both atmospheric chemistry and astrophysics. In the Earth's atmosphere, it enters in the sulfur cycle and it is ubiquitous present in polluted atmospheres, where it is responsible for acid rains. It is also of astrophysical and planetological importance, being present on Venus and in interstellar clouds. In this work the collisional broadening of a number of ν1 ro-vibrational lines of SO2 perturbed by N2, O2 and He are investigated at room temperature in the 9 μm atmospheric region by means of high resolution tunable diode laser (TDL) infrared spectroscopy. From N2- and O2-broadening coefficients, the broadening parameters of sulfur dioxide in air, useful for atmospheric applications, are derived as well. From the present measurements some conclusions on the quantum number dependence of the N2-, O2- and He-broadening coefficients are drawn. While the J dependence is weak for all the perturbers investigated, different trends with Ka are reported. N2-broadening coefficients show a slight decrease with increasing values of Ka, whereas O2 and He broadening cross sections first increase up to Ka″≈6 and then they keep a nearly constant value. A comparison and a brief discussion on the efficiency of self-, N2-, O2- and He-collisional dynamics are given. The data obtained represent a significant analysis on foreign broadening of SO2 useful for atmospheric remote sensing and astrophysical applications.

  13. The influence of bremsstrahlung on electric discharge streamers in N2, O2 gas mixtures

    NASA Astrophysics Data System (ADS)

    Köhn, C.; Chanrion, O.; Neubert, T.

    2017-01-01

    Streamers are ionization filaments of electric gas discharges. Negative polarity streamers propagate primarily through electron impact ionization, whereas positive streamers in air develop through ionization of oxygen by UV photons emitted by excited nitrogen; however, experiments show that positive streamers may develop even for low oxygen concentrations. Here we explore if bremsstrahlung ionization facilitates positive streamer propagation. To discriminate between effects of UV and bremsstrahlung ionization, we simulate the formation of a double headed streamer at three different oxygen concentrations: no oxygen, 1 ppm O2 and 20% O2, as in air. At these oxygen levels, UV-relative to bremsstrahlung ionization is zero, small, and large. The simulations are conducted with a particle-in-cell code in a cylindrically symmetric configuration at ambient electric field magnitudes three times the conventional breakdown field. We find that bremsstrahlung induced ionization in air, contrary to expectations, reduces the propagation velocity of both positive and negative streamers by about 15%. At low oxygen levels, positive streamers stall; however, bremsstrahlung creates branching sub-streamers emerging from the streamer front that allow propagation of the streamer. Negative streamers propagate more readily forming branching sub-streamers. These results are in agreement with experiments. At both polarities, ionization patches are created ahead of the streamer front. Electrons with the highest energies are in the sub-streamer tips and the patches.

  14. Nonstationary effects in ozone generation by barrier discharges in N2/O2 mixtures

    NASA Astrophysics Data System (ADS)

    Zosimov, A. V.; Lunin, V. V.; Samoilovich, V. G.; Abramovskaya, E. A.; Mankelevich, Yu. A.; Poroykov, A. Yu.; Rakhimova, T. V.; Voloshin, D. G.

    2016-08-01

    The yield of ozone in barrier discharges in oxygen-nitrogen mixtures containing 0.001 to 40% of nitrogen is investigated experimentally. Phenomena of the nonstationarity of processes of ozone generation that differ from the known ozone-zero phenomenon (OZP) apparent in the reduced efficiency of ozone generation in very high purity oxygen at long periods (from hours to tens of hours) of ozonator operation are found. It is established that the characteristic times (from minutes to tens of minutes) of ozone attaining stationary values after changes in the discharge parameters indicate slow adjustment of the surface condition of insulators and thus the heterogeneous decay of ozone to more rapidly changing flows of neutral and charged particles from gas discharge plasma on the surfaces of dielectrics. The possibility of such a scenario is confirmed using a new analytical approach and numerical calculations of the plasma-chemical kinetics of N2/O2 mixtures presented in the accompanying theoretical study.

  15. Direct N2H4/H2O2 Fuel Cells Powered by Nanoporous Gold Leaves

    PubMed Central

    Yan, Xiuling; Meng, Fanhui; Xie, Yun; Liu, Jianguo; Ding, Yi

    2012-01-01

    Dealloyed nanoporous gold leaves (NPGLs) are found to exhibit high electrocatalytic properties toward both hydrazine (N2H4) oxidation and hydrogen peroxide (H2O2) reduction. This observation allows the implementation of a direct hydrazine-hydrogen peroxide fuel cell (DHHPFC) based on these novel porous membrane catalysts. The effects of fuel and oxidizer flow rate, concentration and cell temperature on the performance of DHHPFC are systematically investigated. With a loading of ~0.1 mg cm−2 Au on each side, an open circuit voltage (OCV) of 1.2 V is obtained at 80°C with a maximum power density 195 mW cm−2, which is 22 times higher than that of commercial Pt/C electrocatalyst at the same noble metal loading. NPGLs thus hold great potential as effective and stable electrocatalysts for DHHPFCs. PMID:23230507

  16. Respiratory depressant action of tilidine during N2O + O2 anaesthesia.

    PubMed

    Tammisto, T; Tigerstedt, I

    1976-01-01

    The respiratory depressant actions of pethidine and tilidine during anaesthesia were compared in 18 surgical patients anaesthetized with N2O + O2 after thiopental induction. Five minutes after thiopental, 0.5 mg/kg pethidine or 1.5 mg/kg tilidine were each given intravenously to six patients, the remaining six patients serving as controls. Minute ventilation, respiratory rate, end-tidal CO2 and PCO2 from arterialized venous blood were measured up to 30 min. Pethidine caused the following maximal changes: V -0.98 +/- 0.24 (s.e. mean) 1/min, rate -5.5 +/- 0.7/min, CO2ET + 0.7 +/- 0.1 vol % and PCO2 + 5.7 +/- 1.1 mm Hg. These changes occurred within 10 min of the injection.

  17. The calculation of high-temperature equilibrium and nonequilibrium specific heat data for N2, O2 and NO

    NASA Technical Reports Server (NTRS)

    Jaffe, Richard L.

    1987-01-01

    Specific heat data for high-temperature air species are needed to compute the temperature and enthalpy of gas mixtures in aerothermodynamics flowfield calculations. Accurate data are known only for temperatures under 6000 K, but are required for temperatures exceeding 25,000 K. In the present study, CP data are computed for N2, O2 and NO. The calculations are based on summations over all the vibration-rotation energy levels for all known bound electronic states. Estimates are made for the error introduced by the neglect of possible additional high-lying electronic states. In addition, a scheme for the partitioning of the internal energy into vibrational, rotational and electronic contributions is presented which consistently accounts for the nonseparable nature of the various energy modes. The multitemperature specific heat data are recommended for use in nonequilibrium flowfield models.

  18. Etch Properties of Amorphous Carbon Material Using RF Pulsing in the O2/N2/CHF3 Plasma.

    PubMed

    Jeon, Min Hwan; Park, Jin Woo; Yun, Deok Hyun; Kim, Kyong Nam; Yeom, Geun Young

    2015-11-01

    The amorphous carbon layer (ACL), used as the hardmask for the etching of nanoscale semi-conductor materials, was etched using O2/CHF3 in addition to O2/N2 using pulsed dual-frequency capacitively coupled plasmas, and the effects of source power pulsing for different gas combinations on the characteristics of the plasmas and ACL etching were investigated. As the etch mask for ACL, a patterned SiON layer was used. The etch rates of ACL were decreased with the decrease of pulse duty percentage for both O2/N2 and O2/CHF3 due to decrease of the reactive radicals, such as F and O, with decreasing pulse duty percentage. In addition, at the same pulse duty percentage, the etch selectivity of ACL/SiON with O2/CHF3 was also significantly lower than that with O2/N2. However, the etch profiles of ACL with O2/CHF3 was more anisotropic and the etch profiles were further improved with decreasing the pulse duty percentage than those of ACL with O2/N2. The improved anisotropic etch profiles of ACL with decreasing pulse duty percentage for O2/CHF3 were believed to be related to the formation of a more effective passivation layer, such as a thick fluorocarbon layer, on the sidewall of the ACL during the etching with O2/CHF3, compared to the weak C-N passivation layer formed on the sidewall of ACL when using O2/N2.

  19. Influence of Ar/O2/H2O Feed Gas and N2/O2/H2O Environment on the Interaction of Time Modulated MHz Atmospheric Pressure Plasma Jet (APPJ) with Model Polymers

    NASA Astrophysics Data System (ADS)

    Oehrlein, Gottlieb; Luan, Pingshan; Knoll, Andrew; Kondeti, Santosh; Bruggeman, Peter

    2016-09-01

    An Ar/O2/H2O fed time modulated MHz atmospheric pressure plasma jet (APPJ) in a sealed chamber was used to study plasma interaction with model polymers (polystyrene, poly-methyl methacrylate, etc.). The amount of H2O in the feed gas and/or present in the N2, O2, or N2/O2 environment was controlled. Short lived species such as O atoms and OH radicals play a crucial role in polymer etching and surface modifications (obtained from X-ray photoelectron spectroscopy of treated polymers without additional atmospheric exposure). Polymer etching depth for Ar/air fed APPJ mirrors the decay of gas phase O atoms with distance from the APPJ nozzle in air and is consistent with the estimated O atom flux at the polymer surface. Furthermore, whereas separate O2 or H2O admixture to Ar enhances polymer etching, simultaneous addition of O2 and H2O to Ar quenches polymer etching. This can be explained by the mutual quenching of O with OH, H and HO2 in the gas phase. Results where O2 and/or H2O in the environment were varied are consistent with these mechanisms. All results will be compared with measured and simulated species densities reported in the literature. We gratefully acknowledge funding from US Department of Energy (DE-SC0001939) and National Science Foundation (PHY-1415353).

  20. Collision induced broadening of ν1 band and ground state spectral lines of sulfur dioxide perturbed by N2 and O2

    NASA Astrophysics Data System (ADS)

    Ceselin, Giorgia; Tasinato, Nicola; Puzzarini, Cristina; Charmet, Andrea Pietropolli; Stoppa, Paolo; Giorgianni, Santi

    2017-09-01

    To monitor the constituents and trace pollutants of Earth atmosphere and understand its evolution, accurate spectroscopic parameters are fundamental information. SO2 is produced by both natural and anthropogenic sources and it is one of the principal causes of acid rains as well as an important component of fine aerosol particles, once oxidized to sulfate. The present work aims at determining SO2 broadening parameters using N2 and O2 as atmospherically relevant damping gases. Measurements are carried out in the infrared (IR) and mm-/sub-mm wave regions, around 8.8 μm and in the 104 GHz-1.1 THz interval, respectively. IR ro-vibrational transitions are recorded by using a tunable diode laser spectrometer, whereas the microwave spectra are recorded by using a frequency-modulated millimeter-/submillimeter-wave spectrometer. SO2-N2 and SO2-O2 collisional cross sections are retrieved for several ν1 band ro-vibrational transitions of 32S16O2, for some transitions belonging to either ν1 + ν2 - ν2 of 32S16O2 or ν1 of 34S16O2 as well as for about 20 pure rotational transitions in the vibrational ground state of the main isotopic species. From N2- and O2- broadening coefficients the broadening parameters of SO2 in air are derived. The work is completed with the study of the dependence of foreign broadening coefficients on the rotational quantum numbers.

  1. Correcting oceanic O2/Ar-net community production estimates for vertical mixing using N2O observations

    NASA Astrophysics Data System (ADS)

    Cassar, Nicolas; Nevison, Cynthia D.; Manizza, Manfredi

    2014-12-01

    The O2/Ar approach has become a key method to estimate oceanic net community production (NCP). However, in some seasons and regions of the ocean, strong vertical mixing of O2-depleted deepwater introduces a large error into O2/Ar-derived NCP estimates. In these cases, undersaturated-O2/Ar observations have for all intents and purposes been ignored. We propose to combine underway O2/Ar and N2O observations into a composite tracer that is conservative with respect to the influence of vertical mixing on the surface biological O2 inventory. We test the proposed method with an ocean observing system simulation experiment (OSSE) in which we compare N2O-O2/Ar and O2/Ar-only gas flux estimates of NCP to the model-simulated true NCP in the Southern Ocean. Our proof-of-concept simulations show that the N2O-O2/Ar tracer significantly improves NCP estimates when/where vertical mixing is important.

  2. Temperature Dependence of the Collisional Removal of O2(A(sup 3)Sigma(sup +)(sub u), upsilon=9 ) with O2 and N2

    NASA Technical Reports Server (NTRS)

    Hwang, Eunsook S.; Copeland, Richard A.

    1997-01-01

    The temperature dependence of the collisional removal of O2 molecules in the upsilon = 9 level of the A(sup 3)Sigma(sup +)(sub u) electronic state has been studied for the colliders O2 and N2, over the temperature range 150 to 300 K. In a cooled flow cell, the output of a pulsed dye laser excites the O2 to the upsilon = 9 level of the A(sup 3)Sigma(sup +)(sub u) state, and the output of a time-delayed second laser monitors the temporal evolution of this level via a resonance-enhanced ionization. We find the u thermally averaged removal cross section for O2 collisions is constant (approx. 10 A(sup 2)) between room temperature and 200 K, then increases rapidly with decreasing temperature, doubling by 150 K. In contrast, the N2 cross section at 225 K is approx. 8% smaller and gradually increases to a value at 150 K that is approx. 60% larger than the room temperature value. The difference between the temperature dependence of the O2 and N2 collision cross section implies that the removal by oxygen becomes more important at the lower temperatures found in the mesosphere, but removal by N2 still dominates.

  3. Nqrs Data for C6H16I2N2O8 [C6H14N2O2·2(HIO3)] (Subst. No. 0931)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C6H16I2N2O8 [C6H14N2O2·2(HIO3)] (Subst. No. 0931)

  4. Nqrs Data for C6H20I6N2O20 [C6H14N2O2·6(HIO3)] (Subst. No. 0939)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C6H20I6N2O20 [C6H14N2O2·6(HIO3)] (Subst. No. 0939)

  5. Nqrs Data for C6H17I3N2O11 [C6H14N2O2·3(HIO3)] (Subst. No. 0933)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C6H17I3N2O11 [C6H14N2O2·3(HIO3)] (Subst. No. 0933)

  6. Suppressed N2O formation during NH3 selective catalytic reduction using vanadium on zeolitic microporous TiO2

    PubMed Central

    Lee, Seung Gwan; Lee, Hyun Jeong; Song, Inhak; Youn, Seunghee; Kim, Do Heui; Cho, Sung June

    2015-01-01

    Emission of N2O from mobile and off-road engine is now being currently regulated because of its high impact compared to that of CO2, thereby implying that N2O formation from the exhaust gas after-treatment system should be suppressed. Selective catalytic reduction using vanadium supported TiO2 catalyst in mobile and off-road engine has been considered to be major source for N2O emission in the system. Here we have demonstrated that vanadium catalyst supported on zeolitic microporous TiO2 obtained from the hydrothermal reaction of bulk TiO2 at 400 K in the presence of LiOH suppresses significantly the N2O emission compared to conventional VOx/TiO2 catalyst, while maintaining the excellent NOx reduction, which was ascribed to the location of VOx domain in the micropore of TiO2, resulting in the strong metal support interaction. The use of zeolitic microporous TiO2 provides a new way of preparing SCR catalyst with a high thermal stability and superior catalytic performance. It can be also extended further to the other catalytic system employing TiO2-based substrate. PMID:26235671

  7. Suppressed N2O formation during NH3 selective catalytic reduction using vanadium on zeolitic microporous TiO2.

    PubMed

    Lee, Seung Gwan; Lee, Hyun Jeong; Song, Inhak; Youn, Seunghee; Kim, Do Heui; Cho, Sung June

    2015-08-03

    Emission of N2O from mobile and off-road engine is now being currently regulated because of its high impact compared to that of CO2, thereby implying that N2O formation from the exhaust gas after-treatment system should be suppressed. Selective catalytic reduction using vanadium supported TiO2 catalyst in mobile and off-road engine has been considered to be major source for N2O emission in the system. Here we have demonstrated that vanadium catalyst supported on zeolitic microporous TiO2 obtained from the hydrothermal reaction of bulk TiO2 at 400 K in the presence of LiOH suppresses significantly the N2O emission compared to conventional VOx/TiO2 catalyst, while maintaining the excellent NOx reduction, which was ascribed to the location of VOx domain in the micropore of TiO2, resulting in the strong metal support interaction. The use of zeolitic microporous TiO2 provides a new way of preparing SCR catalyst with a high thermal stability and superior catalytic performance. It can be also extended further to the other catalytic system employing TiO2-based substrate.

  8. Suppressed N2O formation during NH3 selective catalytic reduction using vanadium on zeolitic microporous TiO2

    NASA Astrophysics Data System (ADS)

    Lee, Seung Gwan; Lee, Hyun Jeong; Song, Inhak; Youn, Seunghee; Kim, Do Heui; Cho, Sung June

    2015-08-01

    Emission of N2O from mobile and off-road engine is now being currently regulated because of its high impact compared to that of CO2, thereby implying that N2O formation from the exhaust gas after-treatment system should be suppressed. Selective catalytic reduction using vanadium supported TiO2 catalyst in mobile and off-road engine has been considered to be major source for N2O emission in the system. Here we have demonstrated that vanadium catalyst supported on zeolitic microporous TiO2 obtained from the hydrothermal reaction of bulk TiO2 at 400 K in the presence of LiOH suppresses significantly the N2O emission compared to conventional VOx/TiO2 catalyst, while maintaining the excellent NOx reduction, which was ascribed to the location of VOx domain in the micropore of TiO2, resulting in the strong metal support interaction. The use of zeolitic microporous TiO2 provides a new way of preparing SCR catalyst with a high thermal stability and superior catalytic performance. It can be also extended further to the other catalytic system employing TiO2-based substrate.

  9. H2, N2, and O2 metabolism by isolated heterocysts from Anabaena sp. strain CA.

    PubMed Central

    Smith, R L; Kumar, D; Zhang, X K; Tabita, F R; Van Baalen, C

    1985-01-01

    Metabolically active heterocysts isolated from wild-type Anabaena sp. strain CA showed high rates of light-dependent acetylene reduction and hydrogen evolution. These rates were similar to those previously reported in heterocysts isolated from the mutant Anabaena sp. strain CA-V possessing fragile vegetative cell walls. Hydrogen production was observed with isolated heterocysts. The ratio of C2H4 to H2 produced ranged from 0.9 to 1.2, and H2 production exhibited unique biphasic kinetics consisting of a 1 to 2-min burst of hydrogen evolution followed by a lower, steady-state rate of hydrogen production. This burst was found to be dependent upon the length of the dark period immediately preceding illumination and may be related to dark-to-light ATP transients. The presence of 100 nM NiCl2 in the growth medium exerted an effect on both acetylene reduction and hydrogen evolution in the isolated heterocysts from strain CA. H2-stimulated acetylene reduction was increased from 2.0 to 3.2 mumol of C2H4 per mg (dry weight) per h, and net hydrogen production was abolished. A phenotypic Hup- mutant (N9AR) of Anabaena sp. strain CA was isolated which did not respond to nickel. In isolated heterocysts from N9AR, ethylene production rates were the same under both 10% C2H2-90% Ar and 10% C2H2-90% H2 with or without added nickel, and net hydrogen evolution was not affected by the presence of 100 nM Ni2+. Isolated heterocysts from strain CA were shown to have a persistent oxygen uptake of 0.7 mumol of O2 per mg (dry weight) per h, 35% of the rate of whole filaments, at air saturating O2 levels, indicating that O2 impermeability is not a requirement for active heterocysts. PMID:3921524

  10. Observations of the Annual Cycle of Dissolved O2, N2, pCO2 on the Alaskan Shelf

    NASA Astrophysics Data System (ADS)

    Morison, J. H.; McNeil, C. L.; Zhang, J.

    2012-12-01

    To better understand air-sea gas exchange processes in the complex and changing seasonal ice zone of the Arctic, and to better understand carbon/oxygen dynamics over the continental shelf, we deployed a mooring with biogeochemical sensors at about 28 m depth on the Beaufort Shelf at 71.4° N and 152.0° W, just east of Barrow Canyon, in approximately 150 m deep water. We present our first time series observations from September 2010 through October 2011 which include water temperature, salinity, three dissolved gases (O2, N2, and pCO2), and chlorophyll fluorescence. The dataset provide our first look at the annual cycle of the dissolved gases as they are influenced by seasonal changes in ice cover and productivity. The data show the entrance and exit to the region of the warmer summer waters, and chlorophyll blooms. Under-ice changes in gas levels at the depth of the sensors are particularly intriguing. They show a gradual decline and increase in saturation levels of CO2 and O2, respectively. This would normally indicate net productivity; however, photosynthetic solar radiation under the ice cover in winter is very low as was the observed chlorophyll fluorescence. We compare the data to model results to provide more background for interpretation of the data set and compare the timing of the observed versus model chlorophyll blooms.

  11. BiVO4/TiO2(N2) Nanotubes Heterojunction Photoanode for Highly Efficient Photoelectrocatalytic Applications

    NASA Astrophysics Data System (ADS)

    Wang, Rui; Bai, Jing; Li, Yunpo; Zeng, Qingyi; Li, Jinhua; Zhou, Baoxue

    2017-04-01

    We report the development of a novel visible response BiVO4/TiO2(N2) nanotubes photoanode for photoelectrocatalytic applications. The nitrogen-treated TiO2 nanotube shows a high carrier concentration rate, thus resulting in a high efficient charge transportation and low electron-hole recombination in the TiO2-BiVO4. Therefore, the BiVO4/TiO2(N2) NTs photoanode enabled with a significantly enhanced photocurrent of 2.73 mA cm-2 (at 1 V vs. Ag/AgCl) and a degradation efficiency in the oxidation of dyes under visible light. Field emission scanning electron microscopy, X-ray diffractometry, energy-dispersive X-ray spectrometer, and UV-Vis absorption spectrum were conducted to characterize the photoanode and demonstrated the presence of both metal oxides as a junction composite.

  12. O2(b(1)Σg(+)) Quenching by O2, CO2, H2O, and N2 at Temperatures of 300-800 K.

    PubMed

    Zagidullin, M V; Khvatov, N A; Medvedkov, I A; Tolstov, G I; Mebel, A M; Heaven, M C; Azyazov, V N

    2017-09-26

    Rate constants for the removal of O2(b(1)Σg(+)) by collisions with O2, N2, CO2, and H2O have been determined over the temperature range from 297 to 800 K. O2(b(1)Σg(+)) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the b(1)Σg(+)-X(3)Σg(-) fluorescence. The removal rate constants for CO2, N2, and H2O were not strongly dependent on temperature and could be represented by the expressions kCO2 = (1.18 ± 0.05) × 10(-17) × T(1.5) × exp[Formula: see text], kN2 = (8 ± 0.3) × 10(-20) × T(1.5) × exp[Formula: see text], and kH2O = (1.27 ± 0.08) × 10(-16) × T(1.5) × exp[Formula: see text] cm(3) molecule(-1) s(-1). Rate constants for O2(b(1)Σg(+)) removal by O2(X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression kO2 = (7.4 ± 0.8) × 10(-17) × T(0.5) × exp[Formula: see text] cm(3) molecule(-1) s(-1). All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.

  13. Band Gap Tailoring of TiO2 Nanowires by Nitrogen Doping Under N2/Ar Plasma Environment.

    PubMed

    Dhar, J C; Mondal, A; Bhattacharya, S; Singh, N K; Ngangbam, C; Chattopadhyay, K K

    2015-05-01

    Glancing angle deposited TiO2 nanowires (NWs) were doped with nitrogen (N) using plasma-enhanced chemical vapour deposition technique, under the treatment of N2/Ar plasma. A red shift (- 0.51 eV) in the main band transition and oxygen defect related transition (-2.1 eV) was observed for the N doped TiO2 nanowires. The interstitial nitrogen introduces mid-gap levels N (2P) above the O (2P) in the TiO2 forbidden gap. The photoluminescence measurement revealed a small red shift of -7 nm of anatase band gap from N doped TiO2 nanowires due to radiative recombination of carriers from conduction band to the N (2P) trap state. The low frequency Raman peaks at 304 cm(-1) (acoustical phonons with LA mode), 618 cm(-1) (optical phonons with LO modes) and the high frequency peak at 832 cm(-1) was observed from Ti-O-N due to the partial replacement of oxygen molecules by nitrogen into TiO2, during the doping process.

  14. In Situ Multi-Species (O2, N2, Fuel, Other) Fiber Optic Sensor for Fuel Tank Ullage

    NASA Technical Reports Server (NTRS)

    Nguyen, Quang-Viet

    2007-01-01

    A rugged and compact fiber optic sensor system for in situ real-time measurement of nitrogen (N2), oxygen (O2), hydrocarbon (HC) fuel vapors, and other gases has been developed over the past several years at Glenn Research Center. The intrinsically-safe, solid-state fiber optic sensor system provides a 1% precision measurement (by volume) of multiple gases in a 5-sec time window. The sensor has no consumable parts to wear out and requires less than 25 W of electrical power to operate. The sensor head is rugged and compact and is ideal for use in harsh environments such as inside an aircraft fuel tank, or as a feedback sensor in the vent-box of an on-board inert gas generation system (OBIGGS). Multiple sensor heads can be monitored with a single optical detection unit for a cost-effective multi-point sensor system. The present sensor technology is unique in its ability to measure N2 concentration directly, and in its ability to differentiate different types of HC fuels. The present sensor system provides value-added aircraft safety information by simultaneously and directly measuring the nitrogen-oxygen-fuel triplet, which provides the following advantages: (1) information regarding the extent of inerting by N2, (2) information regarding the chemical equivalence ratio, (3) information regarding the composition of the aircraft fuel, and (4) by providing a self-consistent calibration by utilizing a singular sensor for all species. Using the extra information made available by this sensor permits the ignitability of a fuel-oxidizer mixture to be more accurately characterized, which may permit a reduction in the amount of inerting required on a real-time basis, and yet still maintain a fire-safe fuel tank. This translates to an increase in fuel tank fire-safety through a better understanding of the physics of fuel ignition, and at the same time, a reduction in compressed bleed air usage and concomitant aircraft operational costs over the long-run. The present fiber

  15. The effect of N2/+/ recombination on the aeronomic determination of the charge exchange rate coefficient of O/+//2D/ with N2

    NASA Technical Reports Server (NTRS)

    Torr, D. G.; Orsini, N.

    1978-01-01

    The Atmosphere Explorer (AE) data are reexamined in the light of new laboratory measurements of the N2(+) recombination rate coefficient alpha. The new measurements support earlier measurements which yielded values of alpha significantly lower than the AE values. It is found that the values for alpha determined from the satellite data can be reconciled with the laboratory measurements, if the charge exchange rate coefficient for O(+)(2D) with N2 is less than one-quarter of that derived in the laboratory by Rutherford and Vroom (1971).

  16. Collisional Removal of OH (X (sup 2)Pi, nu=7) by O2, N2, CO2, and N2O

    NASA Technical Reports Server (NTRS)

    Knutsen, Karen; Dyer, Mark J.; Copeland, Richard A.

    1996-01-01

    Collisional removal rate constants for the OH (X 2PI, nu = 7) radical are measured for the colliders O2, CO2, and N2O, and an upper limit is established for N2. OH(nu = 4) molecules, generated in a microwave discharge flow cell by the reaction of hydrogen atoms with ozone, are excited to v = 7 by the output of a pulsed infrared laser via direct vibrational overtone excitation. The temporal evolution of the P = 7 population is probed as a function of the collider gas partial pressure by a time-delayed pulsed ultraviolet laser. Fluorescence from the B 21 + state is detected in the visible spectral region.

  17. Kinetics of ozone and nitric oxides in dielectric barrier discharges in O2/NOx and N2/O2/NOx mixtures

    NASA Astrophysics Data System (ADS)

    Stefanovic, I.; Bibinov, N. K.; Deryugin, A. A.; Vinogradov, I. P.; Napartovich, A. P.; Wiesemann, K.

    2001-08-01

    Concentrations of NO, NO2, NO3, N2O5, and O3 were measured by classical absorption spectroscopy in dielectric barrier discharges in flowing O2/NOx and N2/O2/NOx mixtures. The results of measurements in different parts of the discharge chamber and in its exhaust are compared to a numerical zero-dimensional kinetic model and good agreement is found. The experimentally found upper limit of the NOx concentration allowing ozone production is confirmed by the kinetic calculations for both gas mixtures. The rotational temperature of different nitrogen bands was measured by high-resolution emission spectroscopy. The results are explained on the basis of a simplified model and related to the gas temperature in the microdischarge channel and the surrounding gas.

  18. Pressure broadening of ClO by N2 and O2 near 204 and 649 GHz and new frequency measurements between 632 and 725 GHz

    NASA Technical Reports Server (NTRS)

    Oh, J. J.; Cohen, E. A.

    1994-01-01

    The N2 and O2 pressure broadening of the ClO transitions near 204 and 649 GHz have been measured between 200 and 300 K. Oxygen broadening has been measured for the transitions near 278 GHz. The accuracy of the derived air broadening is comparable to that for the air broadening of stable species and is estimated to be within approximately 3% over the entire temperature range. These transitions are currently being used for satellite, balloon, and ground based monitoring of atmospheric ClO, respectively. Some new frequency measurements are reported in the 632 - 725 GHz range. These are in good agreement with previous measurements and predictions.

  19. Thermogravimetric study of the combustion of Tetraselmis suecica microalgae and its blend with a Victorian brown coal in O2/N2 and O2/CO2 atmospheres.

    PubMed

    Tahmasebi, Arash; Kassim, Mohd Asyraf; Yu, Jianglong; Bhattacharya, Sankar

    2013-12-01

    The combustion characteristics of microalgae, brown coal and their blends under O2/N2 and O2/CO2 atmospheres were studied using thermogravimetry. In microalgae combustion, two peaks at 265 and 485°C were attributable to combustion of protein and carbohydrate with lipid, respectively. The DTG profile of coal showed one peak with maximum mass loss rate at 360°C. Replacement of N2 by CO2 delayed the combustion of coal and microalgae. The increase in O2 concentration did not show any effect on combustion of protein at the first stage of microalgae combustion. However, between 400 and 600°C, with the increase of O2 partial pressure the mass loss rate of microalgae increased and TG and DTG curves of brown coal combustion shifted to lower temperature zone. The lowest and highest activation energy values were obtained for coal and microalgae, respectively. With increased microalgae/coal ratio in the blends, the activation energy increased due to synergy effect.

  20. Temperature dependence of the rate coefficient for charge exchange of metastable O/+//2D/ with N2. [in atmosphere

    NASA Technical Reports Server (NTRS)

    Torr, M. R.; Torr, D. G.

    1980-01-01

    Using a data base of aeronomical parameters measured on board the Atmosphere Explorer-C satellite, temperature dependence of the reaction rate coefficient is deduced for the charge exchange of O(+)(2D) with N2. The results indicate the Explorer values determined over the temperature range from 700 to 1900 K are not in conflict with laboratory measurements made at higher temperatures.

  1. Measurements of the O+ plus N2 and O+ plus O2 reaction rates from 300 to 900 K

    NASA Technical Reports Server (NTRS)

    Chen, A.; Johnsen, R.; Biondi, M. A.

    1977-01-01

    Rate coefficients for the O(+) + N2 atom transfer and O(+) + O2 charge transfer reactions are determined at thermal energies between 300 K and 900 K difference in a heated drift tube mass spectrometer apparatus. At 300 K the values K(O(+) + N2) = (1.2 plus or minus 0.1) x 10 to the negative 12 power cubic cm/sec and k(O(+) + O2) = (2.1 plus or minus 0.2) x 10 to the negative 11 power cubic cm/sec were obtained, with a 50% difference decrease in the reaction rates upon heating to 700 K. These results are in good agreement with heated flowing afterglow results, but the O(+) + O2 thermal rate coefficients are systematically lower than equivalent Maxwellian rates inferred by conversion of nonthermal drift tube and flow drift data.

  2. Opposed jet burner studies of hydrogen combustion with pure and N2, NO-contaminated air

    NASA Technical Reports Server (NTRS)

    Guerra, Rosemary; Pellett, Gerald L.; Northam, G. Burton; Wilson, Lloyd G.

    1987-01-01

    A counterflow diffusion flame formed by an argon-bathed tubular-opposed jet burner (OJB) was used to determine the 'blowoff' and 'restore' combustion characteristics for jets of various H2/N2 mixtures and for jets of air contaminated by NO (which normally occurs in high-enthalpy airflows supplied to hypersonic test facilities for scramjet combustors). Substantial divergence of 'blowoff' and 'restore' limits occurred as H2 mass flux, M(H)2, increased, the H2 jet became richer, and the M(air)/M(H2 + N2) ratio increased from 1 to 3 (molar H2/O2 from 1 to 16). Both OJB limits were sensitive to reactant composition. One to six percent NO in air led to significant N2-corrected decreases in the M(H2) values for 'blowoff' (2-8 percent) and 'restore' (6-12 percent) for mole fractions of H2 ranging from 0.5 to 0.95. However, when H2/O2 was held constant, all N2-corrected changes in M(H2) were negligible.

  3. Development of Polysulfone (PSF)-Carbon Molecular Sieve (CMS) Mixed Matrix Membrane (MMM) For O2/N2 Gas Separation

    NASA Astrophysics Data System (ADS)

    Ismail, A. F.; Rahman, W. R.; Aziz, F.

    2009-06-01

    Mixed matrix membranes (MMMs) comprising polysulfone (PSF) Udel® P-1700 and synthesized carbon molecular sieve (CMS) particles (<25 μm) have been fabricated and characterized. CMS were synthesized by using polyacrylonitrile (PAN) as polymer precursor. The casting process was performed at the processing temperature close to Tg of PSF in order to maintain the flexibility of polymer during film formation. This study investigated the effects of CMS loadings (10, 20, 30 and 35 wt%) on the morphology and the gas separation performance of PSF-CMS MMMs. The fabricated MMMs were characterized using TGA, DSC, FESEM and single gas permeation test using high purity O2 and N2. Based on FESEM micrograph, a good polymer-sieve adhesion was achieved in MMMs using the combination of PSF-CMS even at high sieve loading (up to 35 wt%). The formation of `sieve-in-the-cage' morphology in PSF-CMS MMMs has been minimized to a great extend by implementing casting procedure at the operating temperature close to the Tg of polymer matrix. The O2 and N2 permeability for MMMs were increased with increasing CMS loading; while at 20 wt% CMS loading the O2/N2 selectivity attain the highest value which is 5.97 with the O2 permeability of 7.9617 barrers.

  4. Novel measurements of refractive index, density and mid-infrared integrated band strengths for solid O2, N2O and NO2 : N2O4 mixtures

    NASA Astrophysics Data System (ADS)

    Fulvio, D.; Sivaraman, B.; Baratta, G. A.; Palumbo, M. E.; Mason, N. J.

    2009-06-01

    We present novel measurements of the refractive index, density and integrated band strengths of mid-infrared features of solid N2O at 16 K and of NO2 and N2O4 in two frozen NO2:N2O4 mixtures deposited at 16 and 60 K. The refractive index and density measurements were performed also for frozen O2 deposited at 16 K. In this case, the integrated band strength values could not be determined since O2 is a homonuclear molecule and therefore its fundamental mode is not infrared active. The solid samples were analysed by infrared spectroscopy in the 8000.800 cm -1 range. The sample thickness was measured by the interference curve obtained using a He-Ne laser operating at 543 nm. The refractive index at this laser wavelength was obtained, by numerical methods, from the measured amplitude of the interference curve. The density values were obtained using the Lorentz-Lorenz relation. Integrated band strength values were then obtained by a linear fit of the integrated band intensities plotted versus column density values. The astrophysical relevance of these novel measurements is briefly discussed.

  5. Kinetics and mechanism of the formation of water cluster ions from O2(plus) and H2O in He, Ar, N2, and O2 at 296 K. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Howard, C. J.; Bierbaum, V. M.; Rundle, H. W.; Kaufman, F.

    1972-01-01

    The reaction sequence leading from O2(+) to H3O(+)-H2O was examined in He, Ar, N2 and O2 carrier gases in a flowing afterglow system. The rate constants for the reactions were measured and the kinetic analysis for their determination is presented. For M = N2, two new steps involving the formation and reaction of O2(+)-N2 were proposed and examined. The rate constants are discussed and compared with other experimental values.

  6. Kinetic modeling of the formation and growth of inorganic nano-particles during pulverized coal char combustion in O2/N2 and O2/CO2 atmospheres

    DOE PAGES

    Shaddix, Christopher R.; Niu, Yanqing; Hui, Shi'en; ...

    2016-08-01

    In this formation of nano-particles during coal char combustion, the vaporization of inorganic components in char and the subsequent homogeneous particle nucleation, heterogeneous condensation, coagulation, and coalescence play decisive roles. Furthermore, conventional measurements cannot provide detailed information on the dynamics of nano-particle formation and evolution, In this study, a sophisticated intrinsic char kinetics model that considers ash effects (including ash film formation, ash dilution, and ash vaporization acting in tandem), both oxidation and gasification by CO2 and H2O, homogeneous particle nucleation, heterogeneous vapor condensation, coagulation, and and coalescence mechanisms is developed and used to compare the temporal evolution of themore » number and size of nano-particles during coal char particle combustion as a function of char particle size, ash content, and oxygen content in O2/N2 and O2/CO2 atmospheres .« less

  7. Unraveling the importance of surface association to the formation of molecules in a recombining N_2 / O_2 plasma

    NASA Astrophysics Data System (ADS)

    Zijlmans, R.; Welzel, S.; Gabriel, O.; van Helden, J. H.; Ropcke, J.; Schram, D. C.; Engeln, R.

    2008-07-01

    mainly on the gas phase formation of NO, but recognize the importance of the surfaces of the plasma reactor. Also Castillo et al. (2005) conclude in their studies that mainly heterogeneous processes are responsible for the formation of NO. To unravel the contribution of surface related processes to the total kinetics in a low pressure recombining plasma created from mixtures of N_2 and O_2, we measured the abundance of the stable molecules NO, N_2O and NO_2 in the plasma by means of IRMA, which is an IR tunable diode laser absorption system (Ropcke et al. 2000), and mass spectrometry (N_2 and O_2). A simulation, developed in CHEMKIN (2004), is used to investigate the effect of radical-surface interactions on the conversion of the feedstock gases. 2. RESULTS A plasma expansion is created from a flow of 3000 standard cubic centimeters per minute (sccm) argon through a cascaded arc plasma source. A total power of 5 kW (I = 75 A) is used to create the Ar plasma in the arc channel of the source. This plasma expands from the exit of the arc channel into the reactor, which is kept at a pressure of p = 20 Pa or p =100 Pa. A total flow of 1800 sccm of mixtures of N_2 and O_2 is injected directly into the reactor. The molecular abundances of the species formed in the plasma vessel are investigated as function of the ratio of admixed O_2 flow over the total flow of O_2 and N_2. In Figure 1 the symbols denote the measured mole fractions of Ar, N_2, O_2, NO, N_2O and NO_2, which are plotted on a semi-logarithmic scale. All the species are measured with the quadrupole mass spectrometer, while NO and N_2O are also measured by infrared absorption spectroscopy, using the IRMA system (Ropcke et al. 2000). The results of both the mass spectrometry measurements and tunable diode laser absorption spectroscopy measurements showed good agreement (within 10 %). For both pressures the molecules N_2 and O_2 are dominantly present. The abundance of the other types of molecules (NO, NO_2 and N_2O

  8. Synthesis and characterization of amorphous SiO2 nanowires via pulsed laser deposition accompanied by N2 annealing

    NASA Astrophysics Data System (ADS)

    Li, Hui; Guan, Leilei; Xu, Zhuoqi; Zhao, Yu; Sun, Jian; Wu, Jiada; Xu, Ning

    2016-12-01

    Amorphous SiO2 nanowires are successfully fabricated on fused silica substrates covered by nickel/carbon catalyst bilayers via a method of pulsed laser deposition accompanied by annealing in ambient N2. The field emission scanning electron microscopy images show that the optimum annealing temperature for the growth of SiO2 nanowires is about 1200 °C and the grown SiO2 nanowires become denser, longer and more uniform with the increment of annealing duration. The results of transmission electron microscopy and high-resolution transmission electron microscopy show that the grown nanowires are amorphous and have dark spheres on their tops. The analyses of energy dispersive X-ray spectroscopy reveal that the nanowires are composed of SiO2 and the dark spheres on their tops contain little nickel. It is inferred that nickel, carbon and CO are the key elements to promote the SiO2 nanowire growth in the solid-liquid-solid mode. Transmission spectra demonstrate that the as-grown nanowire thin films can have about 94% average transmittance in the range of 350-800 nm, meanwhile the photoluminescence spectra of the as-grown SiO2 nanowire samples show stable ultraviolet emission centered at about 363 nm with a shoulder at about 393 nm.

  9. Low-energy proton stopping power of N2, O2 and water vapor and deviations from Bragg's rule

    NASA Technical Reports Server (NTRS)

    Xu, Y. J.; Khandelwal, G. S.; Wilson, J. W.

    1984-01-01

    A modified local plasma model, based on the works of Lindhard and Winther; and Bethe, Brown, and Walske, is established. The Gordon-Kim model for molecular electron density is used to calculate stopping power of N2, O2, and water vapor for protons of energy ranging from 40 keV to 2.5 MeV, resulting in good agreement with experimental data. Deviations from Bragg's rule are evaluated and are discussed under the present theoretical model.

  10. Nqrs Data for C10H11AuCl4N2O2 (Subst. No. 1239)

    NASA Astrophysics Data System (ADS)

    Chihara, H.; Nakamura, N.

    This document is part of Subvolume A `Substances Containing Ag … C10H15' of Volume 48 `Nuclear Quadrupole Resonance Spectroscopy Data' of Landolt-Börnstein - Group III `Condensed Matter'. It contains an extract of Section `3.2 Data tables' of the Chapter `3 Nuclear quadrupole resonance data' providing the NQRS data for C10H11AuCl4N2O2 (Subst. No. 1239)

  11. Vibration-dissociation coupling in CO, N2 and O2 - An evaluation of analytic transition rate expressions

    NASA Technical Reports Server (NTRS)

    Gonzales, David A.; Varghese, Philip L.

    1993-01-01

    Closed form expressions for inelastic state-to-state and state-specific dissociative rate coefficients for utilization in vibrational master equation studies of shock heated CO, N2, and O2 highly dilute in Ar are considered. The master equation is linearized by neglecting diatom-diatom collisions and recombination. Master equation results indicate that the most significant contribution to dissociation comes from low and mid lying vibrational levels.

  12. Vibration-dissociation coupling in CO, N2 and O2 - An evaluation of analytic transition rate expressions

    NASA Technical Reports Server (NTRS)

    Gonzales, David A.; Varghese, Philip L.

    1993-01-01

    Closed form expressions for inelastic state-to-state and state-specific dissociative rate coefficients for utilization in vibrational master equation studies of shock heated CO, N2, and O2 highly dilute in Ar are considered. The master equation is linearized by neglecting diatom-diatom collisions and recombination. Master equation results indicate that the most significant contribution to dissociation comes from low and mid lying vibrational levels.

  13. Thymidine decomposition induced by low-energy electrons and soft X rays under N2 and O2 atmospheres.

    PubMed

    Alizadeh, Elahe; Sanz, Ana G; Madugundu, Guru S; García, Gustavo; Wagner, J Richard; Sanche, Léon

    2014-06-01

    A novel technique has been employed to investigate the simultaneous damage to DNA components induced by soft X rays (1.5 keV) and low-energy electrons (0-30 eV) in thin films of thymidine deposited on glass and tantalum substrates and irradiated under atmospheric pressure and temperature. The films were surrounded by either an N2 or O2 environment. The formation of four radiation-induced products is reported in this article: base release, 5-hydroxymethyl-2'-deoxyuridine (5-HMdUrd), 5-formyl-2'-deoxyuridine (5-FordUrd) and 5,6-dihydrothymidine (5,6-DHThd). Analysis with LC-MS/MS shows larger damage yields in the samples deposited on tantalum than in those deposited on glass, which is attributed to the interaction of the additional low-energy electrons that are photoemitted from the metal surface. From a comparison of the results obtained from N2 and O2 environment, we report a dramatic effect from 6 O2: an approximately threefold increase in the yield of products, attributed to the reaction of O2 with initial carbon-centered thymidine radicals generated in the film during irradiation.

  14. CoNi@SiO2 @TiO2 and CoNi@Air@TiO2 Microspheres with Strong Wideband Microwave Absorption.

    PubMed

    Liu, Qinghe; Cao, Qi; Bi, Han; Liang, Chongyun; Yuan, Kaiping; She, Wen; Yang, Yongji; Che, Renchao

    2016-01-20

    The synthesis of CoNi@SiO2 @TiO2 core-shell and CoNi@Air@TiO2 yolk-shell microspheres is reported for the first time. Owing to the magnetic-dielectric synergistic effect, the obtained CoNi@SiO2 @TiO2 microspheres exhibit outstanding microwave absorption performance with a maximum reflection loss of -58.2 dB and wide bandwidth of 8.1 GHz (8.0-16.1 GHz, < -10 dB).

  15. N2O seasonal distributions and air-sea exchange in UK estuaries: Implications for the tropospheric N2O source from European coastal waters

    NASA Astrophysics Data System (ADS)

    Barnes, J.; Upstill-Goddard, R. C.

    2011-03-01

    We report measurements of dissolved nitrous oxide (N2O), dissolved inorganic nitrogen, and turbidity in surveys of six UK inner estuaries between February 2000 and October 2002: the Humber, Forth, Tamar, Tyne, Tees, and Tay. We also present dissolved N2O data for the Wash outer estuary from May 1995 and dissolved O2 data for the Forth estuary from June 2001. N2O was always supersaturated relative to air and was highest in the Humber (range 140-6500%) and generally higher at all sites during summer. In estuaries with well defined turbidity maximum zones (TMZs) at low salinity, N2O was maximal in the TMZ, coincident with high NH4+ and/or NO3-. Inspection of the broad relationships between N2O, NH4+, NO3-, NO2-, and O2 revealed a predominantly nitrification source for the N2O in the estuaries studied; denitrification-derived N2O was apparently unimportant and denitrification did not constitute a significant NO3- sink. In the anthropogenically impacted Tees estuary N2O (saturation 140-2000%) was attributed to high NH4+ in sewage and industrial effluent. N2O emissions were thus primarily a function of NH4+ derived from internal resuspension and/or ammonification, or external inputs and were independent of river-borne NO3-. We reevaluated total UK and European estuarine N2O emissions using these and published data, based on an aerially weighted approach that separately identified inner and outer estuaries, and a downward revision of the total European estuarine area used in a recent synthesis. Our revised estimates, ˜1.9 ± 1.2 × 109 g N2O yr-1 for the UK and 6.8 ± 13.2 × 109 g N2O yr-1 for Europe (including UK) are dominated by large (area ˜200-500 km2) anthropogenically impacted macrotidal inner estuaries. By contrast large pristine macrotidal systems, small inner estuaries, and large outer estuaries appear to be comparatively minor N2O sources. The UK estuarine N2O source is <2% of the UK N2O budget. Our revised European estuarine N2O emission is around 2 orders

  16. Long-Term And/Or Seasonal Variation of Suprathermal O2+ and N2+ at Saturn

    NASA Astrophysics Data System (ADS)

    Christon, S. P.; Hamilton, D. C.; Mitchell, D. G.; Krimigis, S. M.; DiFabio, R. D.

    2011-12-01

    The suprathermal minor heavy ion groups O2+ and 28M+ (mixed N2+ and/or CO+) at~32 and ~28 amu/e, respectively, exhibit long-term spatial-temporal variations in Saturn's magnetosphere at ~3-20 Rs from 2004 to 2011. These ~83-167 keV/e ions are the second most abundant ion groups heavier than the water group W+ (O+, OH+, H2O+, and H3O+) measured by the Cassini CHEMS ion spectrometer. O2+ declines by order of ~6-7 relative to W+ from mid-2004 until equinox in mid-2009 and then remains relatively constant. 28M+, initially ~5 times less abundant than O2+, declines by order of ~2 relative to W+ until early-2007 and then remains at lower values with significant variation. After late-2009 28M+/O2+ is ~0.5. The declining O2+ and 28M+ flux occurs as ring plane illumination decreases approaching Saturn's equinox. The main ring atmosphere/ ionosphere is the most likely primary source for the O2+. Titan, Enceladus, Rhea, and the E-ring are candidate sources for the 28M+. Neither O2+ nor 28M+ has begun recovery by mid-2011, arguing for reduced levels this Saturn season. Transition from higher/declining to lower/persistent levels suggests multiple competing components for both ion groups, that is, one component, probably ring-insolation related, is initially dominant and decreases gradually to be masked later by a lower-level component. The relation of the ions' flux generation and modulation by Saturn's moons and rings is addressed.

  17. The Benthic Exchange of O2, N2 and Dissolved Nutrients Using Small Core Incubations

    PubMed Central

    Owens, Michael S.; Cornwell, Jeffrey C.

    2016-01-01

    The measurement of sediment-water exchange of gases and solutes in aquatic sediments provides data valuable for understanding the role of sediments in nutrient and gas cycles. After cores with intact sediment-water interfaces are collected, they are submerged in incubation tanks and kept under aerobic conditions at in situ temperatures. To initiate a time course of overlying water chemistry, cores are sealed without bubbles using a top cap with a suspended stirrer. Time courses of 4-7 sample points are used to determine the rate of sediment water exchange. Artificial illumination simulates day-time conditions for shallow photosynthetic sediments, and in conjunction with dark incubations can provide net exchanges on a daily basis. The net measurement of N2 is made possible by sampling a time course of dissolved gas concentrations, with high precision mass spectrometric analysis of N2:Ar ratios providing a means to measure N2 concentrations. We have successfully applied this approach to lakes, reservoirs, estuaries, wetlands and storm water ponds, and with care, this approach provides valuable information on biogeochemical balances in aquatic ecosystems. PMID:27583833

  18. The Benthic Exchange of O2, N2 and Dissolved Nutrients Using Small Core Incubations.

    PubMed

    Owens, Michael S; Cornwell, Jeffrey C

    2016-08-03

    The measurement of sediment-water exchange of gases and solutes in aquatic sediments provides data valuable for understanding the role of sediments in nutrient and gas cycles. After cores with intact sediment-water interfaces are collected, they are submerged in incubation tanks and kept under aerobic conditions at in situ temperatures. To initiate a time course of overlying water chemistry, cores are sealed without bubbles using a top cap with a suspended stirrer. Time courses of 4-7 sample points are used to determine the rate of sediment water exchange. Artificial illumination simulates day-time conditions for shallow photosynthetic sediments, and in conjunction with dark incubations can provide net exchanges on a daily basis. The net measurement of N2 is made possible by sampling a time course of dissolved gas concentrations, with high precision mass spectrometric analysis of N2:Ar ratios providing a means to measure N2 concentrations. We have successfully applied this approach to lakes, reservoirs, estuaries, wetlands and storm water ponds, and with care, this approach provides valuable information on biogeochemical balances in aquatic ecosystems.

  19. EUV studies of N2 and O2 produced by low energy electron impact

    NASA Technical Reports Server (NTRS)

    Morgan, H. D.; Mentall, J. E.

    1983-01-01

    The emission spectra resulting from electron impact excitation on molecular nitrogen and oxygen in the 500-1200 A spectral region are investigated. Electron energies are from 0 to 300 eV. Numerous bands of N2 are found between 800 and 1000 A. Excitation functions are measured for the NII 916 A, the OI 879 A, and the OII 834 multiplets, and nitrogen band emission. Cross sections were measured at 200 eV for several of the band emissions plus the NI 1135 A, NI 1164 A, NI 1177 A, NII 776 A, NII 1084 A, OI 1152 A, OI 1041 A, OI 999 A, OI 989 A, OI 879 A, OII 834 A, OII 616 A, OII 555 A, OII 539 A, and OII 718 A multiplets.

  20. EUV studies of N2 and O2 produced by low energy electron impact

    NASA Technical Reports Server (NTRS)

    Morgan, H. D.; Mentall, J. E.

    1983-01-01

    The emission spectra resulting from electron impact excitation on molecular nitrogen and oxygen in the 500-1200 A spectral region are investigated. Electron energies are from 0 to 300 eV. Numerous bands of N2 are found between 800 and 1000 A. Excitation functions are measured for the NII 916 A, the OI 879 A, and the OII 834 multiplets, and nitrogen band emission. Cross sections were measured at 200 eV for several of the band emissions plus the NI 1135 A, NI 1164 A, NI 1177 A, NII 776 A, NII 1084 A, OI 1152 A, OI 1041 A, OI 999 A, OI 989 A, OI 879 A, OII 834 A, OII 616 A, OII 555 A, OII 539 A, and OII 718 A multiplets.

  1. Measurements and Modeling of Nitric Oxide Formation in Counterflow, Premixed CH4/O2/N2 Flames

    NASA Technical Reports Server (NTRS)

    Thomsen, D. Douglas; Laurendeau, Normand M.

    2000-01-01

    Laser-induced fluorescence (LIF) measurements of NO concentration in a variety of CH4/O2/N2 flames are used to evaluate the chemical kinetics of NO formation. The analysis begins with previous measurements in flat, laminar, premixed CH4/O2/N2 flames stabilized on a water-cooled McKenna burner at pressures ranging from 1 to 14.6 atm, equivalence ratios from 0.5 to 1.6, and volumetric nitrogen/oxygen dilution ratios of 2.2, 3.1 and 3.76. These measured results are compared to predictions to determine the capabilities and limitations of the comprehensive kinetic mechanism developed by the Gas Research Institute (GRI), version 2.11. The model is shown to predict well the qualitative trends of NO formation in lean-premixed flames, while quantitatively underpredicting NO concentration by 30-50%. For rich flames, the model is unable to even qualitatively match the experimental results. These flames were found to be limited by low temperatures and an inability to separate the flame from the burner surface. In response to these limitations, a counterflow burner was designed for use in opposed premixed flame studies. A new LIF calibration technique was developed and applied to obtain quantitative measurements of NO concentration in laminar, counterflow premixed, CH4/O2/N2 flames at pressures ranging from 1 to 5.1 atm, equivalence ratios of 0.6 to 1.5, and an N2/O2 dilution ratio of 3.76. The counterflow premixed flame measurements are combined with measurements in burner-stabilized premixed flames and counterflow diffusion flames to build a comprehensive database for analysis of the GRI kinetic mechanism. Pathways, quantitative reaction path and sensitivity analyses are applied to the GRI mechanism for these flame conditions. The prompt NO mechanism is found to severely underpredict the amount of NO formed in rich premixed and nitrogen-diluted diffusion flames. This underprediction is traced to uncertainties in the CH kinetics as well as in the nitrogen oxidation chemistry

  2. Spectroscopic studies of MW plasmas containing HMDSO, O2 and N2

    NASA Astrophysics Data System (ADS)

    Nave, Andy; Roepcke, Juergen; Mitschker, Felix; Awakowicz, Peter

    2015-09-01

    The deposition of SiOx layers based on organosilicon plasmas is used to implement advantageous mechanical, electrical, and/or optical properties on various substrates. The development of such coating processes resulting in a wide range of chemical and physical film properties, using hexamethyldisiloxane (HMDSO) as a precursor, has been in the center of interest of various studies. In plasma, the dissociation of HMDSO into a large amount of fragments is a complex chemical phenomenon. The monitoring of the precursor and of formed species is very valuable to understand the plasma chemistry. Infrared absorption spectroscopy based on lead salt lasers and EC Quantum Cascade Laser have been used to monitor the concentrations of HMDSO, and of the reaction products CH4, C2H2, C2H4,C2H6, CO, CO2 and CH3 as a function of the HMDSO/O2 mixture ratio, and the power at various pressures in a MW plasma deposition reactor. Optical emission spectroscopy has been applied as complementary diagnostics to evaluate electron density and electron temperature. Supported by the German Research Foundation within SFB-TR24 and SFB-TR87.

  3. Full CI benchmark calculations on N2, NO, and O2 - A comparison of methods for describing multiple bonds

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1987-01-01

    Full configuration interaction (CI) calculations on the ground states of N2, NO, and O2 using a DZP Gaussian basis are compared with single-reference SDCI and coupled pair approaches (CPF), as well as with CASSCF multireference CI approaches. The CASSCF/MRCI technique is found to describe multiple bonds as well as single bonds. Although the coupled pair functional approach gave chemical accuracy (1 kcal/mol) for bonds involving hydrogen, larger errors occur in the CPF approach for the multiple bonded systems considered here. CI studies on the 1Sigma(g +) state of N2, including all single, double, triple, and quadruple excitations show that triple excitations are very important for the multiple bond case, and accounts for most of the deficiency in the coupled pair functional methods.

  4. Calculated potential surfaces for the reactions: O + N2 yields NO + N and N + O2 yields NO + O

    NASA Technical Reports Server (NTRS)

    Walch, Stephen P.; Jaffe, Richard J.

    1986-01-01

    Complete Active Space SCF/Contracted CI (CASSCF/CCI) calculations, using large Gaussian basis sets, are presented for selected portions of the potential surfaces for the reactions in the Zeldovich mechanism for the conversion of N2 to NO. The N + O2 reaction is exoergic by 32 kcal/mole and is computed to have an early barrier of 10.2 kcal/mole for the (sup 2)A(sup prime) surface and 18.0 kcal/mole for the (sup 4)A(sup prime) surface. The O + N2 reaction is endoergic by 75 kcal/mole. The (sup 3)A(sup double prime) surface is calculated to have a late barrier of 0.5 kcal/mole, while the (sup 3)A(sup prime) surface is calculated to have a late barrier of 14.4 kcal/mole.

  5. O2(X,v=8-22) 300 K quenching rate coefficients for O2 and N2, and O2(x) vibrational distribution from 248 nm O3 photodissociation

    NASA Astrophysics Data System (ADS)

    Park, H.; Slanger, T. G.

    1994-01-01

    Vibrationally excited oxygen (O‡2) is produced in the atmosphere by ozone photodissociation in the 200-300 nm Hartley band. It has been suggested that photoexcitation of O‡2 in the O2 Schumann-Runge bands will lead to predissociation, and autocatalytic production of O3. The resultant new source of atmospheric O3 could help alleviate current discrepancies between observed and modeled O3 profiles. To evaluate this possibility, we have examined two critical factors—the nascent distribution of O‡2 levels for 248 nm photodissociation, near the peak of the Hartley band, and the rate coefficients for their relaxation by O2 and N2. We find that the distribution extends to v=22, close to the thermodynamic limit, with a peak near v=8. The 300 K quenching rate coefficients have been evaluated using a cascade model, in which it is assumed that relaxation by O2 occurs through single-quantum vibration-vibration (V-V) and vibration-translation (V-T) steps. By modeling the relaxation from the top of the distribution downwards, we simultaneously obtain both the quenching rate coefficients and the nascent vibrational distribution. Agreement with new rate coefficient measurements carried out in a state-specific manner is good, as is also true for the comparison with new V-V and V-T calculations. Data from experiments on O‡2 quenching by N2 show that in the v=16-22 range, potentially important in the atmosphere, quenching proceeds up to five times faster than for the case of O2. The hypothesized explanation is that two-quantum V-V transfer, peaking at the resonant condition of O2(v=18-19), is the dominant process. As a consequence, atmospheric quenching of O‡2 for levels above v=14 is basically controlled by N2, and at low stratospheric temperatures, the effect of N2 quenching near v=18 is likely to be 2 orders of magnitude greater than quenching by O2. This unexpected effect probably precludes a significant role for O‡2 photodissociation as a new source of stratospheric

  6. Simultaneous retrieval of the solar EUV flux and neutral thermospheric O, O2, N2, and temperature from twilight airglow

    NASA Technical Reports Server (NTRS)

    Fennelly, J. A.; Torr, D. G.; Richards, P. G.; Torr, M. R.

    1994-01-01

    We present a method to retrieve neutral thermospheric composition and the solar EUV flux from ground-based twilight optical measurements of the O(+) ((exp 2)P) 7320 A and O((exp 1)D) 6300 A airglow emissions. The parameters retrieved are the neutral temperature, the O, O2, N2 density profiles, and a scaling factor for the solar EUV flux spectrum. The temperature, solar EUV flux scaling factor, and atomic oxygen density are first retrieved from the 7320-A emission, which are then used with the 6300-A emission to retrieve the O2 and N2 densities. The retrieval techniques have been verified by computer simulations. We have shown that the retrieval technique is able to statistically retrieve values, between 200 and 400 km, within an average error of 3.1 + or - 0.6% for thermospheric temperature, 3.3 + or - 2.0% for atomic oxygen, 2.3 + or - 1.3% for molecular oxygen, and 2.4 + or - 1.3% for molecular nitrogen. The solar EUV flux scaling factor was found to have a retrieval error of 5.1 + or - 2.3%. All the above errors have a confidence level of 95%. The purpose of this paper is to prove the viability and usefulness of the retrieval technique by demonstrating the ability to retrieve known quantities under a realistic simulation of the measurement process, excluding systematic effects.

  7. Effect of excited nitrogen atoms on inactivation of spore-forming microorganisms in low pressure N2/O2 surface-wave plasma

    NASA Astrophysics Data System (ADS)

    Yang, Xiaoli; Chang, Xijiang; Tei, Reitou; Nagatsu, Masaaki

    2016-06-01

    Using a vacuum ultraviolet (VUV) absorption spectroscopy with a compact low pressure plasma light source, the absolute nitrogen atom density was measured to study its role in the spore inactivation with low pressure N2/O2 gas mixture surface-wave plasmas (SWPs). Self-absorption effect of the resonance emission lines of nitrogen atoms near 120 nm was minimized by optimizing its discharge conditions of the plasma light source. Experimental results showed that excited nitrogen atom densities monotonically decreased with the decrease of N2 gas percentage in N2/O2 gas mixture SWPs, concomitantly with similar decrease of VUV/UV emission intensities of nitrogen atoms and molecules. In the pure N2 gas SWPs, it was confirmed that a dominant lethal factor was VUV/UV emission generated by N2 plasma, while spore etching occurred via physical and chemical interactions with nitrogen species. With an addition of O2 gas, significant spore etching by excited oxygen atoms made it much easier for the VUV/UV photons emitted by nitrogen atoms, N2 and NO molecules to penetrate through the etched spore coats to the core and cause the fatal DNA damage of the microorganisms. As a result, more rapid inactivation was achieved in the middle region of N2/O2 gas mixture ratio, such as 30-80% O2 gas addition, in the present N2/O2 gas mixture SWPs.

  8. Picosecond-TALIF and VUV absorption measurements of absolute atomic nitrogen densities from an RF atmospheric pressure plasma jet with He/O2/N2 gas mixtures

    NASA Astrophysics Data System (ADS)

    West, Andrew; Niemi, Kari; Schröter, Sandra; Bredin, Jerome; Gans, Timo; Wagenaars, Erik

    2015-09-01

    Reactive Oxygen and Nitrogen species (RONS) from RF atmospheric pressure plasma jets (APPJs) are important in biomedical applications as well as industrial plasma processing such as surface modification. Atomic oxygen has been well studied, whereas, despite its importance in the plasma chemistry, atomic nitrogen has been somewhat neglected due to its difficulty of measurement. We present absolute densities of atomic nitrogen in APPJs operating with He/O2/N2 gas mixtures in open air, using picosecond Two-photon Absorption Laser Induced Fluorescence (ps-TALIF) and vacuum ultra-violet (VUV) absorption spectroscopy. In order to apply the TALIF technique in complex, He/O2/N2 mixtures, we needed to directly measure the collisional quenching effects using picosecond pulse widths (32ps). Traditional calculated quenching corrections, used in nanosecond TALIF, are inadequate due to a lack of quenching data for complex mixtures. Absolute values for the densities were found by calibrating against a known density of Krypton. The VUV absorption experiments were conducted on the DESIRS synchrotron beamline using a unique VUV Fourier-transform spectrometer. Atomic nitrogen densities were on the order of 1020 m-3 with good agreement between TALIF and VUV absorption. UK EPSRC grant EP/K018388/1.

  9. Effects of H2O, CO2, and N2 Air Contaminants on Critical Airside Strain Rates for Extinction of Hydrogen-Air Counterflow Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Pellett, G. L.; Wilson, L. G.; Northam, G. B.; Guerra, Rosemary

    1989-01-01

    Coaxial tubular opposed jet burners (OJB) were used to form dish shaped counterflow diffusion flames (CFDF), centered by opposing laminar jets of H2, N2 and both clean and contaminated air (O2/N2 mixtures) in an argon bath at 1 atm. Jet velocities for flame extinction and restoration limits are shown versus wide ranges of contaminant and O2 concentrations in the air jet, and also input H2 concentration. Blowoff, a sudden breaking of CFDF to a stable ring shape, occurs in highly stretched stagnation flows and is generally believed to measure kinetically limited flame reactivity. Restore, a sudden restoration of central flame, is a relatively new phenomenon which exhibits a H2 dependent hysteresis from Blowoff. For 25 percent O2 air mixtures, mole for mole replacement of 25 percent N2 contaminant by steam increased U(air) or flame strength at Blowoff by about 5 percent. This result is consistent with laminar burning velocity results from analogous substitution of steam for N2 in a premixed stoichiometric H2-O2-N2 (or steam) flame, shown by Koroll and Mulpuru to promote a 10 percent increase in experimental and calculated laminar burning velocity, due to enhanced third body efficiency of water in: H + O2 + M yields HO2 + M. When the OJB results were compared with Liu and MacFarlane's experimental laminar burning velocity of premixed stoichiometric H2 + air + steam, a crossover occurred, i.e., steam enhanced OJB flame strength at extinction relative to laminar burning velocity.

  10. Dissociation of N2O on anatase TiO2 (001) surface - The effect of oxygen vacancy and presence of Ag cluster

    NASA Astrophysics Data System (ADS)

    Sowmiya, M.; Senthilkumar, K.

    2016-12-01

    The increase in concentration of nitrous oxide (N2O) in the atmosphere is one of the major contributors to the greenhouse effect, ozone depletion and climate change. Therefore, it is important to decompose harmful N2O molecule into harmless N2. In the present work, we have studied the decomposition of N2O on anatase TiO2 (001) surface using first principle calculations. The results indicates that the N2O molecule is physisorbed on perfect TiO2 surface without any dissociation, and is dissociated into N2 and oxygen on the reduced TiO2 surface. In addition, it has been found that the interaction between N2O and TiO2 is augmented by the presence of Ag cluster on anatase (001) surface. On the basis of Bader charge analysis and electron density difference plot, it has been found that the excess charge in the reduced anatase TiO2 (001) surface is transferred to the adsorbed N2O molecule, which results the weakening of N

  11. Production of simplex RNS and ROS by nanosecond pulse N2/O2 plasma jets with homogeneous shielding gas for inducing myeloma cell apoptosis

    NASA Astrophysics Data System (ADS)

    Liu, Zhijie; Xu, Dehui; Liu, Dingxin; Cui, Qingjie; Cai, Haifeng; Li, Qiaosong; Chen, Hailan; Kong, Michael G.

    2017-05-01

    In this paper, atmospheric pressure N2/O2 plasma jets with homogeneous shielding gas excited by nanosecond pulse are obtained to generate simplex reactive nitrogen species (RNS) and reactive oxygen species (ROS), respectively, for the purpose of studying the simplex RNS and ROS to induce the myeloma cell apoptosis with the same discharge power. The results reveal that the cell death rate by the N2 plasma jet with N2 shielding gas is about two times that of the O2 plasma jet with O2 shielding gas for the equivalent treatment time. By diagnosing the reactive species of ONOO-, H2O2, OH and \\text{O}2- in medium, our findings suggest the cell death rate after plasma jets treatment has a positive correlation with the concentration of ONOO-. Therefore, the ONOO- in medium is thought to play an important role in the process of inducing myeloma cell apoptosis.

  12. The need for fentanyl supplementation of N2O-O2 relaxant anaesthesia in chronic alcoholics.

    PubMed

    Tammisto, T; Tigerstedt, I

    1977-01-01

    In order to find out how the need for analgesic supplementation during N2O-O2-relaxant anaesthesia is affected by chronic alcohol consumption, 82 patients with various known alcohol habits were anaesthetized for gastric or biliary surgery. Muscular relaxation was kept constant with the aid of a peripheral neurostimulator, and fentanyl was given in increments of 0.05-0.1 mg for nociceptive symptoms during the anaesthesia. For induction, alcoholics (annual consumption above 151 pure alcohol) needed significantly more thiopental/kg body weight than social drinkers (1--151 annually) or non-alcoholics (less than 11 annually), and excitative symptoms were more frequent in alcoholics. A positive correlation was found between fentanyl supplementation and alcohol consumption (r = 0.41), non-alcoholics requiring on average 3.8 microng/kg/h of fentanyl, as compared with 6.4 microng/kg/h in alcoholics. This correlation was clearer than that found previously under similar conditions by the authors between halothane supplementation and alcohol consumption (r = 0.20). In both studies the correlation was partly due to the higher incidence of gastric surgery among alcoholics, since gastric surgery itself requires more supplementation. An analysis of the different symptoms pointing to the need for fentanyl supplementation revealed that the simultaneous occurrence of several symptoms and the prevalence of motor responses were more common in alcoholics. In one patient halothane had to be used as well. In other patients no special difficulties were observed, and none of the patients reported dreams or recollections. The results suggest that during N2O-O2-relaxant anaesthesia the demand for fentanyl supplementation is increased by about 70% in chronic alcoholics with a mean annual consumption of 311 pure alcohol.

  13. Mixed ligand Cu(II)N2O2 complexes: biomimetic synthesis, activities in vitro and biological models, theoretical calculations.

    PubMed

    Li, Chen; Yin, Bing; Kang, Yifan; Liu, Ping; Chen, Liang; Wang, Yaoyu; Li, Jianli

    2014-12-15

    Three new mixed ligand Cu(II)N2O2 complexes, namely, [Cu(II)(2-A-6-MBT)2(m-NB)2] (1), [Cu(II)(2-ABT)2(m-NB)2] (2), and [Cu(II)(2-ABT)2(o-NB)2] (3), (2-A-6-MBT = 2-amino-6-methoxybenzothiazole, m-NB = m-nitrobenzoate, 2-ABT = 2-aminobenzothiazole, and o-NB = o-nitrobenzoate), have been prepared by the biomimetic synthesis strategy, and their structures were determined by X-ray crystallography studies and spectral methods. These complexes exhibited the effective superoxide dismutase (SOD) activity and catecholase activity. On the basis of the experimental data and computational studies, the structure-activity relationship for these complexes was investigated. The results reveal that electron-accepting abilities of these complexes and coordination geometries have significant effects on the SOD activity and catecholase activity. Then, we found that 1 and 2 exerted potent intracellular antioxidant capacity in the model of H2O2-induced oxidative stress based on HeLa cervical cancer cells, which were screened out by the cytotoxicity assays of different kinds of cells. Furthermore, 1-3 showed the favorable biocompatibility in two different biological models: Saccharomyces cerevisiae and human vascular endothelial cells. These biological experimental data are indicative of the promising application potential of these complexes in biology and pharmacology.

  14. Technique to retrieve solar EUV flux and neutral thermospheric O, O2, N2, and temperature from airglow measurements

    NASA Technical Reports Server (NTRS)

    Fennelly, J. A.; Germany, G. A.; Torr, D. G.; Richards, P. G.; Torr, M. R.

    1994-01-01

    We describe a method for retrieving neutral thermospheric composition and solar EUV flux from optical measurements of the O(+)(P-2) 732 nm and O(D-1) 630 nm airglow emissions. The parameters retrieved are the neutral temperature, the O, L2, and N2 density profiles, and a scaling factor for the solar EUV flux spectrum. The temperature, solar EUV flux scaling factor, and atomic oxygen density are first retrieved from the 732 nm emission, which are then used with the 630 nm emission to retrieve the O2 and N2 densities. Between the altitudes of 200 and 400 km the retrieval technique is able to statistically retrieve values to within 3.1% for thermospheric temperature, 3.3% for atomic oxygen, 2.3% for molecular oxygen, and 2.4% for molecular nitrogen. The solar EUV flux scaling factor has a retrieval error of 5.1%. We also present the results of retrievals using existing data taken from both groundbased and spacebased instruments. These include airglow data taken by the Visible Airglow Experiment on the Atmospheric Explorer spacecraft and the Imaging Spectrometric Observatory flown on the ATLAS 1 shuttle mission in 1992.

  15. Studies of iron(II) and iron(III) complexes with fac-N2O, cis-N2O2 and N2O3 donor ligands: models for the 2-His 1-carboxylate motif of non-heme iron monooxygenases.

    PubMed

    Cappillino, Patrick J; Miecznikowski, John R; Tyler, Laurie A; Tarves, Paul C; McNally, Joshua S; Lo, Wayne; Kasibhatla, Bala Sundari T; Krzyaniak, Matthew D; McCracken, John; Wang, Feng; Armstrong, William H; Caradonna, John P

    2012-05-14

    Enzymes in the oxygen-activating class of mononuclear non-heme iron oxygenases (MNOs) contain a highly conserved iron center facially ligated by two histidine nitrogen atoms and one carboxylate oxygen atom that leave one face of the metal center (three binding sites) open for coordination to cofactor, substrate, and/or dioxygen. A comparative family of [Fe(II/III)(N(2)O(n))(L)(4-n))](±x), n = 1-3, L = solvent or Cl(-), model complexes, based on a ligand series that supports a facially ligated N,N,O core that is then modified to contain either one or two additional carboxylate chelate arms, has been structurally and spectroscopically characterized. EPR studies demonstrate that the high-spin d(5) Fe(III)g = 4.3 signal becomes more symmetrical as the number of carboxylate ligands decreases across the series Fe(N(2)O(3)), Fe(N(2)O(2)), and Fe(N(2)O(1)), reflecting an increase in the E/D strain of these complexes as the number of exchangeable/solvent coordination sites increases, paralleling the enhanced distribution of electronic structures that contribute to the spectral line shape. The observed systematic variations in the Fe(II)-Fe(III) oxidation-reduction potentials illustrate the fundamental influence of differential carboxylate ligation. The trend towards lower reduction potential for the iron center across the [Fe(III)(N(2)O(1))Cl(3)](-), [Fe(III)(N(2)O(2))Cl(2)](-) and [Fe(III)(N(2)O(3))Cl](-) series is consistent with replacement of the chloride anions with the more strongly donating anionic O-donor carboxylate ligands that are expected to stabilize the oxidized ferric state. This electrochemical trend parallels the observed dioxygen sensitivity of the three ferrous complexes (Fe(II)(N(2)O(1)) < Fe(II)(N(2)O(2)) < Fe(II)(N(2)O(3))), which form μ-oxo bridged ferric species upon exposure to air or oxygen atom donor (OAD) molecules. The observed oxygen sensitivity is particularly interesting and discussed in the context of α-ketoglutarate-dependent MNO enzyme

  16. O2 absorption for measurements of sea surface air pressure

    NASA Astrophysics Data System (ADS)

    Lin, B.; Hu, Y.

    2006-12-01

    Currently, sea surface air pressure measurements can only be obtained from in situ observations including buoy and dropsonde measurements, which are sparse in spatial coverage and expensive to implement. There are no operational remote sensing methods available even in experimental stages. The study considers use absorption features of microwave radiative transfer, especially the differential O2 absorption for active microwave systems working at 50-56 GHz bands, to fill the observational gap. The numerical simulation results for homogeneous sea surface backgrounds show that the rms errors of the instantaneous surface pressure estimates can be as low as 4 mb. This considered active system will have great potential for weather observations and other meteorological applications, especially for forecasts of hurricanes. Case studies show that with the remotely sensed sea surface barometric pressure data, the errors of hurricane center pressure, the most important indicator of hurricane intensity, in weather prediction models would reduce from about 48 mb to about 1.5 mb. The increased accuracy is about 1/3 of whole range of possible variations of hurricane center pressure. The uncertainties in the weather model predicted landfall positions or tracks of hurricanes also shrink greatly from ~350 km to within 100 km.

  17. 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.

  18. Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures

    PubMed Central

    Liu, Shurong; Berns, Anne E.; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

    2017-01-01

    Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH2OH) to nitrous oxide (N2O) is a possible mechanism of N2O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO2) and organic matter (OM) content of soil as well as soil pH are important control variables of N2O formation in the soil. But until now, their combined effect on abiotic N2O formation from NH2OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO2 and OM, respectively, and quantified the interactive effects of the three variables on the NH2OH-to-N2O conversion ratio (RNH2OH-to-N2O). Furthermore, the effect of OM quality on RNH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO2 and OM on RNH2OH-to-N2O. In general, increasing MnO2 and decreasing pH increased RNH2OH-to-N2O, while increasing OM content was associated with a decrease in RNH2OH-to-N2O. Organic matter quality also affected RNH2OH-to-N2O. However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials. PMID:28145407

  19. Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures

    NASA Astrophysics Data System (ADS)

    Liu, Shurong; Berns, Anne E.; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

    2017-02-01

    Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH2OH) to nitrous oxide (N2O) is a possible mechanism of N2O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO2) and organic matter (OM) content of soil as well as soil pH are important control variables of N2O formation in the soil. But until now, their combined effect on abiotic N2O formation from NH2OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO2 and OM, respectively, and quantified the interactive effects of the three variables on the NH2OH-to-N2O conversion ratio (RNH2OH-to-N2O). Furthermore, the effect of OM quality on RNH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO2 and OM on RNH2OH-to-N2O. In general, increasing MnO2 and decreasing pH increased RNH2OH-to-N2O, while increasing OM content was associated with a decrease in RNH2OH-to-N2O. Organic matter quality also affected RNH2OH-to-N2O. However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials.

  20. Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures.

    PubMed

    Liu, Shurong; Berns, Anne E; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

    2017-02-01

    Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH2OH) to nitrous oxide (N2O) is a possible mechanism of N2O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO2) and organic matter (OM) content of soil as well as soil pH are important control variables of N2O formation in the soil. But until now, their combined effect on abiotic N2O formation from NH2OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO2 and OM, respectively, and quantified the interactive effects of the three variables on the NH2OH-to-N2O conversion ratio (RNH2OH-to-N2O). Furthermore, the effect of OM quality on RNH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO2 and OM on RNH2OH-to-N2O. In general, increasing MnO2 and decreasing pH increased RNH2OH-to-N2O, while increasing OM content was associated with a decrease in RNH2OH-to-N2O. Organic matter quality also affected RNH2OH-to-N2O. However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials.

  1. Self-, N2-, O2-broadening coefficients and line parameters of HFC-32 for ν7 band and ground state transitions from infrared and microwave spectroscopy

    NASA Astrophysics Data System (ADS)

    Tasinato, Nicola; Turchetto, Arianna; Puzzarini, Cristina; Stoppa, Paolo; Pietropolli Charmet, Andrea; Giorgianni, Santi

    2014-09-01

    Hydrofluorocarbons have been used as replacement gases of chlorofluorocarbons, since the latter have been phased out by the Montreal Protocol due to their environmental hazardous ozone-depleting effects. This is also the case of difluoromethane (CH2F2, HFC-32), which nowadays is widely used in refrigerant mixtures together with CF3CH3, CF3CH2F, and CF3CHF2. Due to its commercial use, in the last years, the atmospheric concentration of HFC-32 has increased significantly. However, this molecule presents strong absorptions within the 8-12 μm atmospheric window, and hence it is a greenhouse gas which contributes to global warming. Although over the years several experimental and theoretical investigations dealt with the spectroscopic properties of CH2F2, up to now pressure broadening coefficients have never been determined. In the present work, the line-by-line parameters of CH2F2 are retrieved for either ground state or ν7 band transitions by means of microwave (MW) and infrared (IR) absorption spectroscopy, respectively. In particular, laboratory experiments are carried out on 9 pure rotational transitions of the ground state and 26 ro-vibrational transitions belonging to the ν7 band lying around 8.2 μm within the atmospheric region. Measurements are carried out at room temperature on self-perturbed CH2F2 as well as on CH2F2 perturbed by N2 and O2. The line shape analysis leads to the first determination of self-, N2-, O2-, and air-broadening coefficients, and also of line intensities (IR). Upon comparison, broadening coefficients of ground state transitions are larger than those of the ν7 band, and no clear dependence on the rotational quantum numbers can be reported. The obtained results represent basic information for the atmospheric modelling of this compound as well as for remote sensing applications.

  2. Synthesis, spectral characterization, molecular modeling and antimicrobial activity of new potentially N2O2 Schiff base complexes

    NASA Astrophysics Data System (ADS)

    Adly, Omima M. I.; Taha, Ali; Fahmy, Shery A.

    2013-12-01

    Metal complexes of a new potentially tetradentate symmetrical Schiff base ligand (H2L) with Cu(II), Ni(II), Co(II), VO(IV), Zn(II), Cd(II), Ce(III), Fe(III) and UO2(VI) metal ions have been synthesized and characterized based on their elemental analyses, spectral (IR, UV-Vis, 1H NMR and mass spectra), magnetic and molar conductance studies as well as thermal gravimetric analysis (TGA). The synthesized complexes have the general formula [MHxL(H2O)yXn]: x = 0-1, y = 0-4 and n = 0-1; where: L = dianion of 6-hydroxy-5-[N-(2-{[(1E)-1-(6-hydroxy-2,4-dioxo-3,4-dihydro-2H-1,3-thiazin-5-yl)ethylidene]amino}ethyl) ethanimidoyl]-2H-1,3-thiazine-2,4(3H)-dione and X = nitrate or sulphate anion. The ligand behaves as diabasic tetradentate N2O2 sites, except in cases of Co(II), VO(IV) and UO2(VI) metal ions, it behaves as monobasic tetradentate Schiff base ligand. The metal complexes exhibited square planar, square-pyramidal and octahedral geometrical arrangements except for Ce(III) and UO2(VI) complexes, they are octa-coordinated. The Coats-Redfern equation was used to calculate the kinetic and thermodynamic parameters for the different thermal decomposition stages of some complexes. Structural parameters of the ligand and its metal complexes have been theoretically computed on the basis of semiemperical PM3 level, and the results were correlated with their experimental data. The antimicrobial activities of the ligand and its metal complexes were tested against some Gram-positive and Gram-negative bacteria; and fungus strain and the results were discussed.

  3. Comparative study of CO 2 formation in CO oxidation by O 2, NO and N 2O on Pd(1 1 0) surface using infrared chemiluminescence

    NASA Astrophysics Data System (ADS)

    Nakao, Kenji; Ito, Shin-ichi; Tomishige, Keiichi; Kunimori, Kimio

    2006-09-01

    The infrared (IR) chemiluminescence spectra of CO 2 were measured during steady-state CO oxidation by O 2, NO and N 2O over Pd(1 1 0) surface. Kinetics of these reactions were studied using a molecular-beam reaction system, and the order of the activity was as follows: CO + O 2 > CO + NO > CO + N 2O. From the analysis of the IR emission spectra, it is found that the antisymmetric vibrational mode of CO 2 was more excited in the case of the CO + O 2 and CO + N 2O reactions, in contrast, the bending vibrational mode was more excited in the case of the CO + NO reaction. These results suggest that the activated complex of CO 2 in the CO + NO reaction has more bent structure than those in the CO + O 2 and CO + N 2O reactions. The reason of this different behavior of the CO + NO reaction is discussed based on higher structure-sensitivity of the CO + NO reaction than the CO + O 2 and CO + N 2O reactions.

  4. First-principles calculation on electronic structure and optical property of BaSi2O2N2:Eu2+ phosphor

    NASA Astrophysics Data System (ADS)

    Tong, Zhi-Fang; Wei, Zhan-Long; Xiao, Cheng

    2017-04-01

    The crystal structure, electronic structure and optical properties of BaSi2O2N2:Eu2+ with varying Eu doping concentrations are computed by the density functional theory (DFT) and compared with experimental results. The results show that the lattice parameters of primitive cells of Ba1-xSi2O2N2:Eux become smaller and Eu-N bond length shortens as Eu concentration increases. The band structure of Ba1-xSi2O2N2:Eux exhibits a direct optical band gap and it's propitious to luminescence. The energy differences from the lowest Eu 5d state to the lowest Eu 4f state decrease with increasing Eu concentrations. The analysis of simulative absorption spectra indicates that the electron transition from Eu 4f states to 5d states of both Eu and Ba atoms contributes to the absorption of Ba1-xSi2O2N2:Eux. Under the coupling effect between Eu and Ba, Ba in BaSi2O2N2 exhibits longer wavelength absorption and increases absorption efficiency. The emission wavelength is deduced by measuring energy differences from the lowest Eu 5d state to the lowest Eu 4f state, and the result is in good agreement with experimental value within experimental Eu2+ doping range.

  5. Structural and functional mimic of galactose oxidase by a copper complex of a sterically demanding [N2O2] ligand.

    PubMed

    John, Alex; Shaikh, Mobin M; Ghosh, Prasenjit

    2008-06-07

    A structural and functional mimic of the galactose oxidase (GOase) enzyme active-site by a copper complex supported over a sterically demanding ligand having [N2O2] donor sites is reported. Specifically, the binding of the histidine (496 and 581) and tyrosine (272 and 495) residues to the copper center in a square-pyramidal fashion in the active-site of galactose oxidase (GOase) enzyme has been modeled in a copper complex, ([(3-tert-butyl-5-methyl-2-hydoxybenzyl)(3'-tert-butyl-5'-methyl-2'-oxobenzyl)(2-pyridylmethyl)]amine)Cu(OAc)) (1b), stabilized over a sterically demanding ligand in which the two phenolate-O atoms mimicked the tyrosine binding while an amine-N and pyridyl-N atoms emulated the histidine binding to the metal center, similar to that in the enzyme active-site. Furthermore, the copper complex 1b is found to be an effective functional model of the enzyme as it efficiently catalyzed the chemoselective oxidation of primary alcohols to aldehydes in high turnover numbers under ambient conditions. An insight into the nature of the active-species was obtained by EPR and CV studies, which in conjunction with the DFT studies, revealed that the active-species is an anti-ferromagnetically coupled diamagnetic radical cation, (1)1b+, obtained by one electron oxidation at the equatorial phenolate-O atom of the ligand in the 1b complex.

  6. A SnO2-Based Cathode Catalyst for Lithium-Air Batteries.

    PubMed

    Mei, Delong; Yuan, Xianxia; Ma, Zhong; Wei, Ping; Yu, Xuebin; Yang, Jun; Ma, Zi-Feng

    2016-05-25

    SnO2 and SnO2@C have been successfully synthesized with a simple hydrothermal procedure combined with heat treatment, and their performance as cathode catalysts of Li-air batteries has been comparatively evaluated and discussed. The results show that both SnO2 and SnO2@C are capable of catalyzing oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) at the cathode of Li-air batteries, but the battery with SnO2@C displays better performance due to its unique higher conductivity, larger surface area, complex pore distribution, and huge internal space.

  7. Novel chemical vapor deposition process of ZnO films using nonequilibrium N2 plasma generated near atmospheric pressure with small amount of O2 below 1%

    NASA Astrophysics Data System (ADS)

    Nose, Yukinori; Yoshimura, Takeshi; Ashida, Atsushi; Uehara, Tsuyoshi; Fujimura, Norifumi

    2016-05-01

    We propose a novel chemical vapor deposition (CVD) process of ZnO films involving a nonequilibrium N2 plasma generated near atmospheric pressure with small O2 concentration (O2%) below 1%. In the optical emission (OE) spectra of the plasma, OE lines corresponding to the NO-γ system ( A 2 Σ + → X 2 Πγ + ) were observed, despite the only introduced gases being N2 and O2; these vanish at an O2% of more than 1%. ZnO films were grown on a glass substrate placed in the plasma at a growth temperature of as low as 200 °C and at an O2% of below 1% in the presence of the NO-γ system. This plasma yielded almost the same growth rate for ZnO films as O2 plasma including atomic O radicals that are often observed in low-pressure O2 plasma, suggesting that some highly reactive oxidant was sufficiently generated in such a small O2%. ZnO films synthesized using this plasma exhibited excellent ( 0001 ) preferred orientation without other diffractions such as 10 1 ¯ 1 diffraction, and with an optical bandgap of 3.30 eV. Based on the analyses of the plasma and the exhaust gases, the coexistence state of NO-γ and O3 should be essential and useful for the decomposition and oxidation of Zn source material in the proposed CVD process.

  8. Effects of H2O, CO2, and N2 air contaminants on critical airside strain rates for extinction of hydrogen-air counterflow diffusion flames

    NASA Technical Reports Server (NTRS)

    Pellett, G. L.; Northam, G. B.; Wilson, L. G.; Guerra, Rosemary

    1989-01-01

    Dish-shaped counterflow diffusion flames centered by opposing laminar jets of H2 and clean and contaminant O2/N2 mixtures in an argon bath at 1 atm were used to study the effects of contaminants on critical airside strain. The jet velocities for both flame extinction and restoration are found for a wide range of contaminant and O2 concentrations in the air jet. The tests are also conducted for a variety of input H2 concentrations. The results are compared with those from several other studies.

  9. Effects of H2O, CO2, and N2 air contaminants on critical airside strain rates for extinction of hydrogen-air counterflow diffusion flames

    NASA Technical Reports Server (NTRS)

    Pellett, G. L.; Northam, G. B.; Wilson, L. G.; Guerra, Rosemary

    1989-01-01

    Dish-shaped counterflow diffusion flames centered by opposing laminar jets of H2 and clean and contaminant O2/N2 mixtures in an argon bath at 1 atm were used to study the effects of contaminants on critical airside strain. The jet velocities for both flame extinction and restoration are found for a wide range of contaminant and O2 concentrations in the air jet. The tests are also conducted for a variety of input H2 concentrations. The results are compared with those from several other studies.

  10. A kinetic study of Mg+ and Mg-containing ions reacting with O3, O2, N2, CO2, N2O and H2O: implications for magnesium ion chemistry in the upper atmosphere.

    PubMed

    Whalley, Charlotte L; Martín, Juan C Gómez; Wright, Timothy G; Plane, John M C

    2011-04-07

    Reactions between Mg(+) and O(3), O(2), N(2), CO(2) and N(2)O were studied using the pulsed laser photo-dissociation at 193 nm of Mg(C(5)H(7)O(2))(2) vapour, followed by time-resolved laser-induced fluorescence of Mg(+) at 279.6 nm (Mg(+)(3(2)P(3/2)-3(2)S(1/2))). The rate coefficient for the reaction Mg(+) + O(3) is at the Langevin capture rate coefficient and independent of temperature, k(190-340 K) = (1.17 ± 0.19) × 10(-9) cm(3) molecule(-1) s(-1) (1σ error). The reaction MgO(+) + O(3) is also fast, k(295 K) = (8.5 ± 1.5) × 10(-10) cm(3) molecule(-1) s(-1), and produces Mg(+) + 2O(2) with a branching ratio of (0.35 ± 0.21), the major channel forming MgO(2)(+) + O(2). Rate data for Mg(+) recombination reactions yielded the following low-pressure limiting rate coefficients: k(Mg(+) + N(2)) = 2.7 × 10(-31) (T/300 K)(-1.88); k(Mg(+) + O(2)) = 4.1 × 10(-31) (T/300 K)(-1.65); k(Mg(+) + CO(2)) = 7.3 × 10(-30) (T/300 K)(-1.59); k(Mg(+) + N(2)O) = 1.9 × 10(-30) (T/300 K)(-2.51) cm(6) molecule(-2) s(-1), with 1σ errors of ±15%. Reactions involving molecular Mg-containing ions were then studied at 295 K by the pulsed laser ablation of a magnesite target in a fast flow tube, with mass spectrometric detection. Rate coefficients for the following ligand-switching reactions were measured: k(Mg(+)·CO(2) + H(2)O → Mg(+)·H(2)O + CO(2)) = (5.1 ± 0.9) × 10(-11); k(MgO(2)(+) + H(2)O → Mg(+)·H(2)O + O(2)) = (1.9 ± 0.6) × 10(-11); k(Mg(+)·N(2) + O(2)→ Mg(+)·O(2) + N(2)) = (3.5 ± 1.5) × 10(-12) cm(3) molecule(-1) s(-1). Low-pressure limiting rate coefficients were obtained for the following recombination reactions in He: k(MgO(2)(+) + O(2)) = 9.0 × 10(-30) (T/300 K)(-3.80); k(Mg(+)·CO(2) + CO(2)) = 2.3 × 10(-29) (T/300 K)(-5.08); k(Mg(+)·H(2)O + H(2)O) = 3.0 × 10(-28) (T/300 K)(-3.96); k(MgO(2)(+) + N(2)) = 4.7 × 10(-30) (T/300 K)(-3.75); k(MgO(2)(+) + CO(2)) = 6.6 × 10(-29) (T/300 K)(-4.18); k(Mg(+)·H(2)O + O(2)) = 1.2 × 10(-27) (T/300 K)(-4.13) cm

  11. Carbon-based air electrodes carrying MnO 2 in zinc-air batteries

    NASA Astrophysics Data System (ADS)

    Wei, Zidong; Huang, Wenzhang; Zhang, Shengtao; Tan, Jun

    Catalysts prepared from the carbon black impregnated with manganous nitrate solution and then heated at temperature from 270°C to 450°C were investigated. It was found that the impregnated catalysts heated at temperature of 340°C exhibited the best catalytic activity for oxygen reduction in alkaline electrolyte. It was also found that the XRD spectra of pyrolytic MnO 2 from manganous nitrate over 340°C were different from those below 340°C. The enhanced catalysis of air electrodes was ascribed to the formation of MnO 2 crystal with d-value of 2.72 Å as the impregnated-catalysts was heated at temperature of 340°C. The other factors in preparation of air electrodes were also discussed.

  12. Co-Adsorption of O2 and CO on Au2(-) : Infrared Photodissociation Spectroscopy and Theoretical Study of [Au2 O2 (CO)n ](-) (n=2-6).

    PubMed

    Liu, Hao; Xing, Xiaopeng; Wang, Xuefeng; Qu, Hui; Wang, Guan-Jun; Zhou, Ming-Fei

    2016-02-01

    The co-adsorption of O2 and CO on anionic sites of gold species is considered as a crucial step in the catalytic CO oxidation on gold catalysts. In this regard, the [Au2 O2 (CO)n ](-) (n=2-6) complexes were prepared by using a laser vaporization supersonic ion source and were studied by using infrared photodissociation spectroscopy in the gas phase. All the [Au2 O2 (CO)n ](-) (n=2-6) complexes were characterized to have a core structure involving one CO and one O2 molecule co-adsorbed on Au2(-) with the other CO molecules physically tagged around. The CO stretching frequency of the [Au2 O2 (CO)](-) core ion is observed around ν˜ =2032-2042 cm(-1) , which is about 200 cm(-1) higher than that in [Au2 (CO)2 ](-) . This frequency difference and the analyses based on density functional calculations provide direct evidence for the synergy effect of the chemically adsorbed O2 and CO. The low lying structures with carbonate group were not observed experimentally because of high formation barriers. The structures and the stability (i.e., the inertness in a sense) of the co-adsorbed O2 and CO on Au2(-) may have relevance to the elementary reaction steps on real gold catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Catalytic wet air oxidation of phenol over CeO2-TiO2 catalyst in the batch reactor and the packed-bed reactor.

    PubMed

    Yang, Shaoxia; Zhu, Wanpeng; Wang, Jianbing; Chen, Zhengxiong

    2008-05-30

    CeO2-TiO2 catalysts are prepared by coprecipitation method, and the activity and stability in the catalytic wet air oxidation (CWAO) of phenol are investigated in a batch reactor and packed-bed reactor. CeO2-TiO2 mixed oxides show the higher activity than pure CeO2 and TiO2, and CeO2-TiO2 1/1 catalyst displays the highest activity in the CWAO of phenol. In a batch reactor, COD and TOC removals are about 100% and 77% after 120 min in the CWAO of phenol over CeO2-TiO2 1/1 catalyst at reaction temperature of 150 degrees C, the total pressure of 3 MPa, phenol concentration of 1000 mg/L, and catalyst dosage of 4 g/L. In a packed-bed reactor using CeO2-TiO2 1/1 particle catalyst, over 91% COD and 80% TOC removals are obtained at the reaction temperature of 140 degrees C, the air total pressure of 3.5 MPa, the phenol concentration of 1000 mg/L for 100 h continue reaction. Leaching of metal ions of CeO2-TiO2 1/1 particle catalyst is very low during the continuous reaction. CeO2-TiO2 1/1 catalyst exhibits the excellent activity and stability in the CWAO of phenol.

  14. Opposed jet burner studies of effects of CO, CO2, and N2 air-contaminants on hydrogen-air diffusion flames

    NASA Technical Reports Server (NTRS)

    Guerra, Rosemary; Pellett, Gerald L.; Northam, G. Burton; Wilson, Lloyd G.

    1987-01-01

    The blowoff/restore characteristics for jets of various H2/N2 mixtures opposed to jets of air contaminated by N2, CO, and CO2 have been determined using a counterflow diffusion flame formed by a tubular opposed jet burner. Both blowoff and restore limits are found to be sensitive to fuel and air composition. Empirically derived variations in the limits of the average mass flux of incoming H2 with percent contaminant, at fixed incoming fuel and H2/O2 inputs, are used to quantify the effects of oxygen dilution, flame augmentation, and flame retardation by N2, CO, and CO2 contaminants. The implications of the results are discussed.

  15. Opposed jet burner studies of effects of CO, CO2, and N2 air-contaminants on hydrogen-air diffusion flames

    NASA Technical Reports Server (NTRS)

    Guerra, Rosemary; Pellett, Gerald L.; Northam, G. Burton; Wilson, Lloyd G.

    1987-01-01

    The blowoff/restore characteristics for jets of various H2/N2 mixtures opposed to jets of air contaminated by N2, CO, and CO2 have been determined using a counterflow diffusion flame formed by a tubular opposed jet burner. Both blowoff and restore limits are found to be sensitive to fuel and air composition. Empirically derived variations in the limits of the average mass flux of incoming H2 with percent contaminant, at fixed incoming fuel and H2/O2 inputs, are used to quantify the effects of oxygen dilution, flame augmentation, and flame retardation by N2, CO, and CO2 contaminants. The implications of the results are discussed.

  16. Influence of alternative cations distribution in AgxLi96-x-LSX on dehydration kinetics and its selective adsorption performance for N2 and O2

    NASA Astrophysics Data System (ADS)

    Panezai, Hamida; Sun, Jihong; Jin, Xiaoqi

    2016-12-01

    Adsorption characteristics of pure gases N2 and O2 on various silver exchanged low silica X-type (AgxLi96-x-LSX) zeolites were investigated. The equilibrium adsorption isotherms of N2 and O2 were measured at 273 and 298 K. Textual and structural properties of parent and resultant AgxLi96-x-LSX were characterized by XRD, BET surface area, and SEM techniques. Kinetics of their thermal dehydration were studied by exploiting thermogravimetric and differential data (TG-DTG) obtained at three heating rates (5, 10 and 15 K) using two model-free (Kissinger and Flynn-Wall-Ozawa) and one model fitting (Coats-Redfern) methods. Forty one mechanism functions were used to evaluate kinetic triplet (activation energy, frequency factor, and most probable mechanism/model) for different stages of dehydration. Results revealed that the impact of very small content of silver on the adsorption of N2 is pronounced and attributed to weak chemical bonds formed between N2 and Ag+ clusters due to strong adsorption of N2 at low pressure, whereas O2 adsorption is affected to a negligible extent. In addition, the N2/O2 adsorption selectivity shows unexpected low values for Ag87.08Li7.94Na0.98-LSX with higher Ag+ content (91.00 %), which might be due to low crystalline water content as well as Ag+ clusters located at SIII sites. N2 adsorption strongly depends on temperature as higher adsorption occurs at low temperature 273 K as compared to 298 K.

  17. Kinetics of organic molecules in pulsed plasmas of nitrogen or N2/O2 mixtures at near atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Pasquiers, S.; Blin-Simiand, N.; Magne, L.

    2013-12-01

    In plasmas of atmospheric gases, the kinetics of some aliphatic organic molecules belonging to the hydrocarbons (propene, propane), aldehydes (acetaldehyde) and ketones (acetone) families were studied using a photo-triggered discharge (homogeneous plasma). It was shown that quenchings of N2 metastable states, A\\,^{3}\\Sigma_{u}^{+} and the group of singlets a'\\,^{1}\\Sigma_{u}^{-} , a 1Πg and w 1Δu, are important processes for the decomposition of such molecules. It plays a fundamental role in the nitrogen plasma, but it is also present in air. At low temperature, the oxidation reactions by the oxygen atom or by the hydroxyl radical are not always sufficiently effective to induce an increase of the molecule decomposition when oxygen is added to the nitrogen/organic mixture. For most cases, quenching processes appear purely dissociative. However, recent results obtained for propene lead to the conclusion that a non-dissociative exit route could exist. The quenching of the singlet states induces a break of the double bound C = O for the acetaldehyde and acetone molecules. Some kinetic analogies appear between filamentary and homogeneous plasmas, which could be very useful to get a comprehensive understanding of the physico-chemical processes in dielectric barriers or corona discharges used for various applications.

  18. Laser-induced fluorescence measurements of nitric oxide in laminar C2H6/O2/N2 flames at high pressure

    NASA Technical Reports Server (NTRS)

    Reisel, John R.; Carter, Campbell D.; Laurendeau, Normand M.

    1993-01-01

    Quantitative measurements of nitric oxide in C2H6/O2/N2 flames at 1-9 atm were successfully carried out using laser-induced fluorescence. The location of maximum NO concentration is found to shift towards leaner equivalence ratios with increasing pressure. Details of the experimental apparatus and measurement procedure are described.

  19. Sediment-water fluxes of dissolved inorganic carbon, O2,nutrients, and N2 from the hypoxic region of the Louisianacontinental shelf

    EPA Science Inventory

    Sediment fluxes of dissolved inorganic carbon (DIC), O2, nutrients, and N2 (denitrification) were measured on the Louisiana Continental Shelf during six cruises from 2005 to 2007. On each cruise, three to seven stations were occupied in regions of the shelf that experience summer...

  20. Sediment-water fluxes of dissolved inorganic carbon, O2,nutrients, and N2 from the hypoxic region of the Louisianacontinental shelf

    EPA Science Inventory

    Sediment fluxes of dissolved inorganic carbon (DIC), O2, nutrients, and N2 (denitrification) were measured on the Louisiana Continental Shelf during six cruises from 2005 to 2007. On each cruise, three to seven stations were occupied in regions of the shelf that experience summer...

  1. Response to suxamethonium during propofol-fentanyl-N2O/O2 anaesthesia in a patient with active myasthenia gravis receiving long-term anticholinesterase therapy.

    PubMed

    Vanlinthout, L E; Robertson, E N; Booij, L H

    1994-06-01

    We describe the effect of repeated suxamethonium doses during propofol-fentanyl-N2O/O2 anaesthesia in a 29-year-old woman with active myasthenia gravis receiving chronic pyridostigmine therapy. Despite adequate pre-operative pseudocholinesterase activity, suxamethonium resistance occurred. Neither bradycardia nor residual neuromuscular block were seen after repeated doses of suxamethonium.

  2. Nanosize Control on Porous β-MnO2 and Their Catalytic Activity in CO Oxidation and N2O Decomposition

    PubMed Central

    Ren, Yu; Ma, Zhen; Dai, Sheng

    2014-01-01

    A major challenge in the synthesis of porous metal oxides is the control of pore size and/or wall thickness that may affect the performance of these materials. Herein, nanoporous β-MnO2 samples were prepared using different hard templates, e.g., ordered mesoporous silica SBA-15 and KIT-6, disordered mesoporous silica, and colloidal silica. These samples were characterized by Powder X-Ray Diffraction (PXRD), Transmission Electron Microscopy (TEM), and N2 adsorption-desorption. The pore size distribution of β-MnO2 was tuned by the different hard templates and their preparation details. Catalytic activities in CO oxidation and N2O decomposition were tested and the mesoporous β-MnO2 samples demonstrated superior catalytic activities compared with their bulk counterpart. PMID:28788635

  3. Superconductivity at 33-37 K in A L n2Fe4As4O2 (A =Kand Cs;L n =lanthanides)

    NASA Astrophysics Data System (ADS)

    Wu, Si-Qi; Wang, Zhi-Cheng; He, Chao-Yang; Tang, Zhang-Tu; Liu, Yi; Cao, Guang-Han

    2017-09-01

    We have synthesized ten iron oxyarsenides, K L n2Fe4As4O2 (L n =Gd,Tb,Dy, and Ho) and Cs L n2Fe4As4O2 (L n =Nd,Sm,Gd,Tb,Dy, and Ho) , with the aid of the lattice-match approach. The resultant compounds possess hole-doped conducting double FeAs layers [AFe4As4] 2 - that are separated by the insulating [Ln2O2] 2 + slabs. Measurements of electrical resistivity and dc magnetic susceptibility demonstrate bulk superconductivity at Tc=33 -37 K. We find that Tc correlates with the axial ratio c /a for all 12442-type superconductors discovered. Also, Tc tends to increase with the lattice mismatch, implying that lattice instability plays a role in the enhancement of superconductivity.

  4. [Catalytic wet air oxidation of phenol with Ru/ZrO2-CeO2 catalyst].

    PubMed

    Wang, Jian-bing; Zhu, Wan-peng; Wang, Wei; Yang, Shao-xia

    2007-07-01

    Wet air oxidation of phenol with Ru/ZrO2-CeO2 was systematically investigated and results showed that Ru/ZrO2-CeO2 could significantly increase the removal of COD and phenol. At the reaction temperature of 170 degrees C and pressure of 3MPa, about 99% COD and 100% phenol was removed respectively after 120 min. The optimal conditions were: reaction temperature, 170 degrees C; reaction pressure, 3 MPa; catalyst dosage, 5 g/L; agitator speed, 500 r/min. By analyzing intermediates, a simplified scheme of phenol oxidation was brought out. It includes two main steps. The first step is the production of organic acids, which is fast. The second step is the oxidation of organic acid, in which the oxidation of acetic acid is slow. Complete oxidation of acetic acid needs high temperature at which the radicals assault the C-H bond of a carbon and acetic acid is oxidized into carbon dioxide and water through formic acid.

  5. Photocatalytic decomposition of N2O over TiO2/g-C3N4 photocatalysts heterojunction

    NASA Astrophysics Data System (ADS)

    Kočí, K.; Reli, M.; Troppová, I.; Šihor, M.; Kupková, J.; Kustrowski, P.; Praus, P.

    2017-02-01

    TiO2/g-C3N4 photocatalysts with the various TiO2/g-C3N4 weight ratios from 1:2 to 1:6 were fabricated by mechanical mixing in water suspension followed by calcination. Pure TiO2 was prepared by thermal hydrolysis and pure g-C3N4 was prepared from commercial melamine by thermal annealing at 620 °C. All the nanocomposites were characterized by X-ray powder diffraction, UV-vis diffuse reflectance spectroscopy, Raman spectroscopy, infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, photoelectrochemical measurements and nitrogen physisorption. The prepared mixtures along with pure TiO2 and g-C3N4 were tested for the photocatalytic decomposition of nitrous oxide under UVC (λ = 254 nm), UVA (λ = 365 nm) and Vis (λ > 400 nm) irradiation. The TiO2/g-C3N4 nanocomposites showed moderate improvement compared to pure g-C3N4 but pure TiO2 proved to be a better photocatalyst under UVC irradiation. However, under UVA irradiation conditions, the photocatalytic activity of TiO2/g-C3N4 (1:2) nanocomposite exhibited an increase compared to pure TiO2. Nevertheless, further increase of g-C3N4 amount leads/led to a decrease in reactivity. These results are suggesting the nanocomposite with the optimal weight ratio of TiO2 and g-C3N4 have shifted absorption edge energy towards longer wavelengths and decreased the recombination rate of charge carriers compared to pure g-C3N4. This is probably due to the generation of heterojunction on the TiO2/g-C3N4 interface.

  6. Heterogeneous interaction of SiO2 with N2O5: aerosol flow tube and single particle optical levitation-Raman spectroscopy studies.

    PubMed

    Tang, M J; Camp, J C J; Rkiouak, L; McGregor, J; Watson, I M; Cox, R A; Kalberer, M; Ward, A D; Pope, F D

    2014-09-25

    Silica (SiO2) is an important mineral present in atmospheric mineral dust particles, and the heterogeneous reaction of N2O5 on atmospheric aerosol is one of the major pathways to remove nitrogen oxides from the atmosphere. The heterogeneous reaction of N2O5 with SiO2 has only been investigated by two studies previously, and the reported uptake coefficients differ by a factor of >10. In this work two complementary laboratory techniques were used to study the heterogeneous reaction of SiO2 particles with N2O5 at room temperature and at different relative humidities (RHs). The uptake coefficients of N2O5, γ(N2O5), were determined to be (7.2 ± 0.6) × 10(-3) (1σ) at 7% RH and (5.3 ± 0.8) × 10(-3) (1σ) at 40% RH for SiO2 particles, using the aerosol flow tube technique. We show that γ(N2O5) determined in this work can be reconciled with the two previous studies by accounting for the difference in geometric and BET derived aerosol surface areas. To probe the particle phase chemistry, individual micrometer sized SiO2 particles were optically levitated and exposed to a continuous flow of N2O5 at different RHs, and the composition of levitated particles was monitored online using Raman spectroscopy. This study represents the first investigation into the heterogeneous reactions of levitated individual SiO2 particles as a surrogate for mineral dust. Relative humidity was found to play a critical role: while no significant change of particle composition was observed by Raman spectroscopy during exposure to N2O5 at RH of <2%, increasing the RH led to the formation of nitrate species on the particle surface which could be completely removed after decreasing the RH back to <2%. This can be explained by the partitioning of HNO3 between the gas and adsorbed phases. The atmospheric implications of this work are discussed.

  7. Oxygen Selective Membranes for Li-Air (O2) Batteries

    PubMed Central

    Crowther, Owen; Salomon, Mark

    2012-01-01

    Lithium-air (Li-air) batteries have a much higher theoretical energy density than conventional lithium batteries and other metal air batteries, so they are being developed for applications that require long life. Water vapor from air must be prevented from corroding the lithium (Li) metal negative electrode during discharge under ambient conditions, i.e., in humid air. One method of protecting the Li metal from corrosion is to use an oxygen selective membrane (OSM) that allows oxygen into the cell while stopping or slowing the ingress of water vapor. The desired properties and some potential materials for OSMs for Li-air batteries are discussed and the literature is reviewed. PMID:24958173

  8. Collisional Removal of O2 (c(sup 1) Sigma(sup-)(sub u), nu=9) by O2, N2, and He

    NASA Technical Reports Server (NTRS)

    Copeland, Richard A.; Knutsen, Karen; Onishi, Marc E.; Yalcin, Talat

    1996-01-01

    The collisional removal Of 02 molecules in selected vibrational levels of the c state is studied using a two-laser double-resonance technique. The output of the first laser excites the 02 to nu = 9 or 10 of the c Sigma - state, and the ultraviolet output of the second laser monitors specific rovibrational levels via resonance-enhanced ionization. The temporal evolution of the c Sigma u state vibrational level is observed by scanning the time delay between the two pulsed lasers. As the rate constants for 02 and N2 are similar in magnitude, N2 collisions dominate the removal rate in the earth's atmosphere. For v= 10 colliding with 02, we find a removal rate constant that is 2-5 times that for v=9 and that single quantum collision cascade is an important pathway for removal.

  9. Phase stability and magnetic behavior of hexagonal phase of N2-O2 system with kagome lattice under high pressure and low temperature

    NASA Astrophysics Data System (ADS)

    Akahama, Y.; Ishihara, D.; Yamashita, H.; Fujihisa, H.; Hirao, N.; Ohishi, Y.

    2016-08-01

    The pressure-temperature (P -T ) phase diagram of N2-O2 mixture with a composition of N2-48 mol % O2 has been investigated using x-ray diffraction and the phase stability of a hexagonal phase (space group: P 6 /mmm), with the kagome lattice examined under high-pressure and low-temperature conditions. While the phase appears as a low-temperature phase of the cubic phase (P m 3 n ) with the structure of γ -O2 or δ -N2 and is stable in a wide range of pressures and temperatures, it transforms to lower symmetry monoclinic or orthorhombic phases at lower temperature, accompanied with a distortion of the kagome lattice. Based on Rietveld refinements, the monoclinic and orthorhombic phases are found to be in the P 21/a and Cmmm space groups, respectively. In magnetization measurements, a magnetic transition is observed with a relatively large drop of magnetization, corresponding to the cubic-to-hexagonal phase transition. This suggests that the hexagonal phase has a certain magnetic ordered state that arises from the molecular magnetic moment of O2.

  10. The 2140 cm-1 (4.673 microns) solid CO band: the case for interstellar O2 and N2 and the photochemistry of nonpolar interstellar ice analogs

    NASA Technical Reports Server (NTRS)

    Elsila, J.; Allamandola, L. J.; Sandford, S. A.

    1997-01-01

    The infrared spectra of CO frozen in nonpolar ices containing N2, CO2, O2, and H2O and the UV photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140 cm-1 (4.673 microns) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing nonpolar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices. The N2 and O2 absorptions at 2328 cm-1 (4.296 microns) and 1549 cm-1 (6.456 microns), respectively, are also shown. The best matches between the narrow interstellar band and the feature in the laboratory spectra of nonpolar ices are for samples which contain comparable amounts of N2, O2, CO2, and CO. Co-adding the CO band from an N2:O2:CO2:CO = 1:5:1/2:1 ice with that of an H2O:CO = 20:1 ice provides an excellent fit across the entire interstellar CO feature. The four-component, nonpolar ice accounts for the narrow 2140 cm-1 portion of the feature which is associated with quiescent regions of dense molecular clouds. Using this mixture, and applying the most recent cosmic abundance values, we derive that between 15% and 70% of the available interstellar N is in the form of frozen N2 along several lines of sight toward background stars. This is reduced to a range of 1%-30% for embedded objects with lines of sight more dominated by warmer grains. The cosmic abundance of O tied up in frozen O2 lies in the 10%-45% range toward background sources, and it is between 1% and 20% toward embedded objects. The amount of oxygen tied up in CO and CO2 frozen in nonpolar ices can be as much as 2%-10% toward background sources and on the order of 0

  11. Morphological modification of alpha-MnO2 catalyst for use in Li/air batteries.

    PubMed

    Park, Min-Sik; Kim, Jae-Hun; Kim, Ki Jae; Jeong, Goojin; Kim, Young-Jun

    2013-05-01

    Single crystal alpha-MnO2 nanowires and nanopowders have been successfully synthesized in order to facilitate a comparison of their catalytic activity for use in Li-air batteries. The importance of the morphological modification of the alpha-MnO2 catalyst for facilitating electrochemical reactions between Li and O2 is addressed. Distinctive catalytic activity of alpha-MnO2 is observed, which is in line with its different morphologies. The catalytic activity significantly affects the reversible capacity of Li-air batteries. A high aspect ratio, large surface area and good dispersibility of alpha-MnO2 in the nanowire form are advantageous providing larger active surfaces for promoting the fundamental reactions in Li-air batteries. We also introduce a robustly designed air-electrode composed of highly porous carbon and nanostructured alpha-MnO2 catalysts, with employs a metal foam current collector to ensure sufficient air-permeability and to maximize electronic conduction during cycles. Our suggestions should prove helpful in forming a basis for further investigations in developing advanced Li-air batteries.

  12. Theoretical study of CO and O2 adsorption and CO oxidation on linear-shape gold molecules (LGMn) (n=2, 4, 8, 16, and 24)

    NASA Astrophysics Data System (ADS)

    Ohkawa, Tetsuya; Kuramoto, Kei

    2016-09-01

    Density functional theory is used to study the effect of increase of the number of Au atom in the adsorption of CO and O2 as well as CO oxidation on anionic, neutral, and cationic Linear-shape Gold Molecules (LGMn) (n=2, 4, 8, 16, and 24). The more the number of Au atom increases, the more the adsorption energies of CO lower and larger in the cationic and anionic LGMnCO complexes, respectively. In contrast, the adsorption energies of both CO and O2 on neutral LGMn exhibit approximately constant values. There are little differences of both adsorption energies and net charge of CO and O2 on the number of Au atom in LGM regardless of each charge state. This indicates that the charge state of LGM plays a less important role for the adsorption of CO and O2 with increase of the number of Au atom in LGM. The trend of the overall activation energies of reaction pathway is switched between LGM-14 and LGM-18 with increase of the number of Au atom in LGM, and OC-OO intermediate of the initial state in n-1LGM (n=8, 16, and 24) are unstable compared to the separated reactants (LGMn, CO, O2). These are caused by the values of charge of O2 of OC-OO intermediate.

  13. Air detoxification with nanosize TiO2 aerosol tested on mice.

    PubMed

    Besov, A S; Krivova, N A; Vorontsov, A V; Zaeva, O B; Kozlov, D V; Vorozhtsov, A B; Parmon, V N; Sakovich, G V; Komarov, V F; Smirniotis, P G; Eisenreich, N

    2010-01-15

    A method for fast air purification using high concentration aerosol of TiO(2) nanoparticles is evaluated in a model chemical catastrophe involving toxic vapors of diisopropyl fluorophosphate (DFP). Mice are used as human model in a closed 100 dm(3) chamber. Exposure of mice to 37 ppm of DFP vapor for 15 min resulted in acute poisoning. Spraying TiO(2) aerosol in 2 min after the start of exposure to DFP vapors resulted in quick removal of DFP vapors from the chamber's air. Animals did not show signs of poisoning after the decontamination experiment and exposure to TiO(2) aerosol alone. Reactive oxygen species (ROS) and antioxidant activity (AOA) of mice blood plasma were measured for animals exposed to sound of aerosol generator, DFP vapors, TiO(2) aerosol and DFP vapors+TiO(2) aerosol. Reduced ROS and increased AOA were found for mice exposure to sound, DFP and TiO(2) aerosol. Exposure to DFP and decontamination with TiO(2) nanoparticles resulted in decreased AOA in 48 h following the exposure. The results suggest that application of TiO(2) aerosol is a powerful method of air purification from toxic hydrolysable compounds with moderate health aftermaths and requires further study and optimization.

  14. The Dependence of Quenching Rate Coefficients for Singlet and Triplet States of n2 and o2 on Vibrational and Translational Temperatures

    NASA Astrophysics Data System (ADS)

    Kirillov, Andrey

    We apply Landau-Zener and Rosen-Zener approximations to obtain analytical formulas for the calculation of quenching rate coefficients of electronically excited states of N2 and O2. This method has allowed us to estimate contributions of intramolecular and intermolecular electron energy transfer processes in the quenching. Using a modified Treanor distribution on vibrational levels for in ground state molecules we have investigated an influence of the vibrational excitation on the rate coefficients. Special attention is paid to energy transfer processes related with the afterglow in laboratory discharges. It is found that there is the influence of vibrational temperature on the coefficients. A dependence of the rate coefficients on translational temperature is studied for few states of N2 and O2. It is shown that for some states there is good agreement of results of theoretical calculations with available experimental data.

  15. Self-, N2, O2, H2, Ar, and He broadening in the nu3 band Q branch of CH4

    NASA Technical Reports Server (NTRS)

    Pine, A. S.

    1992-01-01

    Self-, N2-, O2-, H2-, Ar-, and He-broadening coefficients, pressure shifts, and integrated intensities have been measured for most transitions in the Q branch of the nu3 fundamental band of methane using a difference-frequency laser spectrometer. A systematic dependence of the broadening coefficients on the tetrahedral symmetry species and order index is observed with striking similarities for N2, O2, and Ar and for H2 and He buffer gases. Comparison with earlier measurements on other bands and branches of methane indicates very little vibrational, branch, or carbon isotope dependence. Dicke narrowing is evident at intermediate pressures, yielding an average narrowing coefficient and an optical diffusion constant for each gas mixture.

  16. Role of Fluxes in Optimizing the Optical Properties of Sr0.95Si2O2N2:0.05Eu2+ Green-Emitting Phosphor

    PubMed Central

    Liu, Lihong; Xie, Rong-Jun; Zhang, Chenning; Hirosaki, Naoto

    2013-01-01

    Chlorides of NH4Cl and SrCl2 and fluorides of AlF3 and SrF2 were added to raw materials acting as the flux for preparing the SrSi2O2N2:Eu2+ phosphor. The effects of the fluxes on the phase formation, particle morphology, particle size, and photoluminescence properties were investigated. The results revealed that particle size, particle morphology and photoluminescence intensity were largely dominated by the type of the flux material and its adding amount. The chloride-based flux was found to favor the formation of the SrSi2O2N2:Eu2+ phase. Among the chloride-based fluxes, the sample added with the SrCl2 flux presented the narrow particle distribution and cleaner surface, with enhanced emission intensity and an increased external quantum efficiency by 68% and 22%, respectively, compared with those of the sample without any flux adding. PMID:28811413

  17. Inactivation of Gram-Negative Bacteria by Low-Pressure RF Remote Plasma Excited in N2-O2 Mixture and SF6 Gases.

    PubMed

    Al-Mariri, Ayman; Saloum, Saker; Mrad, Omar; Swied, Ghayath; Alkhaled, Bashar

    2013-12-01

    The role of low-pressure RF plasma in the inactivation of Escherichia coli O157, Klebsiella pneumoniae, Proteus mirabilis, and Enterobacter sakazakii using N2-O2 and SF6 gases was assessed. 1×10(9) colony-forming units (CFUs) of each bacterial isolate were placed on three polymer foils. The effects of pressure, power, distance from the source, and exposure time to plasma gases were optimized. The best conditions to inactivate the four bacteria were a 91%N2-9%O2 mixture and a 30-minute exposure time. SF6 gas was more efficient for all the tested isolates in as much as the treatment time was reduced to only three minutes. Therefore, low-pressure plasma could be used to sterilize heat and/or moisture-sensitive medical instruments.

  18. Tuning the afterglow plasma composition in Ar/N2/O2 mixtures: characteristics of a flowing surface-wave microwave discharge system

    NASA Astrophysics Data System (ADS)

    Kutasi, Kinga; Noël, Cédric; Belmonte, Thierry; Guerra, Vasco

    2016-10-01

    A self-consistent kinetic model is used to study the possibility of tuning the plasma composition in the afterglow of a flowing surface-wave microwave discharge by the different discharge and system parameters in the case of 90%Ar-10%(N2-O2) and N2-O2 mixtures. The afterglow system consists of a 0.5 cm diameter quartz tube of 50 cm in length—where the discharge is generated and the early-afterglow develops—and an afterglow reactor. The plasma composition is studied at the end of the discharge plasma column and at the reactor inlet as a function of the N2:O2 ratio for selected conditions, which are set with the system parameters and are illustrated in the experimental set-up. The validity of the model used is proven by the agreement of the calculated atomic densities with those measured by mass spectrometry. Due to the pressure drop along the tube, the position of the discharge (which also defines the lengths of the early-afterglow, t aft) and the discharge pressure (p dis) can be set with the position of the wave coupler—surfatron—along the tube at a constant gas flow rate (which defines the pressure in the reactor, p reac). It is shown that the relative densities of species at the end of plasma column, which constitute the initial condition for the afterglow, depend on the discharge pressure. Therefore, at a constant gas flow rate with the position of the surfatron the plasma composition in the reactor is changing due to the variation of both the p dis and t aft. The evolution of the plasma composition is also studied when both the surfatron’s position and the gas flow rate are changed, realizing conditions (i) with the same p dis, and different t aft and p reac, and (ii) with the same t aft, and different p dis and p reac. Comparing the N2-O2 binary and the ternary mixtures, it is shown that the atomic densities obtained in the binary mixtures can be reproduced in ternary mixtures with different N2:O2 ratios. Furthermore, according to the spectra

  19. Theoretical views on activation of methane catalyzed by Hf2+ and oxidation of CO (x(1)Σ(+)) by N2O (x(1)Σ(+)) Catalyzed by HfO2+ and TaO2+.

    PubMed

    Nian, Jingyan; Tie, Lu; Wang, Ben; Guo, Zhiguang

    2013-09-12

    The mechanisms of activation of CH4 catalyzed by (1/3)Hf(2+) and oxidation of CO by N2O catalyzed by (1/3)HfO(2+) or (2/4)TaO(2+) have been investigated using the B3LYP level of theory. For the activation of methane, the TSR (two-state reactivity) mechanism has been certified through the spin-orbit coupling (SOC) calculation and the Landau-Zener-type model. In the vicinity of the minimum energy crossing point (MECP), SOC equals 900.23 cm(-1) and the probability of intersystem crossing is approximately 0.62. Spin inversion makes the activation barrier decline from 1.63 to 0.57 eV. NBO analysis demonstrates that empty 6s and 5d orbitals of the Hf atom play the major role for the activation of C-H bonds. Finally, CH4 dehydrogenates to produce Hf-CH2(2+). For oxidation of CO by N2O catalyzed by HfO(2+) or TaO(2+), the covalent bonds between transition metal atoms and the oxygen atom restrict the freedom of valence electrons. Therefore, they are all SSR (single-state reactivity). The oxygen atom is directly extracted during the course of oxygen transfer, and its microscopic essence has been discussed. The detailed kinetic information of two catalytic cycles has been calculated by referencing the "energetic span (δE)" model. Finally, TOF(HfO(2+))/TOF(TaO(2+)) = 2.7 at 298.15 K, which has a good consistency with the experimental result.

  20. Differential cross sections for scattering of 0.5-, 1.5-, and 5.0 keV oxygen atoms by He, N2, and O2

    NASA Technical Reports Server (NTRS)

    Schafer, D. A.; Newman, J. H.; Smith, K. A.; Stebbings, R. F.

    1987-01-01

    This paper reports measurements of absolute scattering cross sections, differential in angle, for collisions of ground-state oxygen atoms with He, N2, and O2. Data are presented for scattering of 0.5-, 1.5-, and 5.0-keV oxygen-atom projectiles in the range of laboratory frame angles between 0.06 and 5 deg. These measurements provide information relevant to calculations of the aeronomic consequences of O(+) precipitation in the earth's upper atmosphere.

  1. Synthesis, antioxidant activities of the nickel(II), iron(III) and oxovanadium(IV) complexes with N2O2 chelating thiosemicarbazones.

    PubMed

    Bal-Demirci, Tülay; Sahin, Musa; Ozyürek, Mustafa; Kondakçı, Esin; Ulküseven, Bahri

    2014-05-21

    The nickel(II), iron(III) and oxovanadium(IV) complexes of the N2O2 chelating thiosemicarbazones were synthesized using 4-hydroxysalicyladehyde-S-methylthiosemicarbazone and R1-substitute-salicylaldehyde (R1: 4-OH, H) in the presence of Ni(II), Fe(III), VO(IV) ions by the template reaction. The structures of the thiosemicarbazone complexes were characterized by FT-IR, (1)H NMR, elemental, ESI-MS and APCI-MS analysis. The synthesized compounds were screened for their antioxidant capacity by using the cupric reducing antioxidant capacity (CUPRAC) method. Trolox equivalent antioxidant capacity (TEAC) of iron(III) complex, 1c, was measured to be higher than that of the other complexes. Other parameters of antioxidant activity (scavenging effects on •OH, O2(•-) and H2O2) of these compounds were also determined. All the compounds have shown encouraging ROS scavenging activities.

  2. OH3- and O2H5- double Rydberg anions: Predictions and comparisons with NH4- and N2H7-

    NASA Astrophysics Data System (ADS)

    Melin, Junia; Ortiz, J. V.

    2007-07-01

    A low barrier in the reaction pathway between the double Rydberg isomer of OH3- and a hydride-water complex indicates that the former species is more difficult to isolate and characterize through anion photoelectron spectroscopy than the well known double Rydberg anion (DRA), tetrahedral NH4-. Electron propagator calculations of vertical electron detachment energies (VEDEs) and isosurface plots of the electron localization function disclose that the transition state's electronic structure more closely resembles that of the DRA than that of the hydride-water complex. Possible stabilization of the OH3- DRA through hydrogen bonding or ion-dipole interactions is examined through calculations on O2H5- species. Three O2H5- minima with H-(H2O)2, hydrogen-bridged, and DRA-molecule structures resemble previously discovered N2H7- species and have well separated VEDEs that may be observable in anion photoelectron spectra.

  3. Atmospheric CO2, δ(O2/N2), APO and oxidative ratios from aircraft flask samples over Fyodorovskoye, Western Russia

    NASA Astrophysics Data System (ADS)

    van der Laan, S.; van der Laan-Luijkx, I. T.; Rödenbeck, C.; Varlagin, A.; Shironya, I.; Neubert, R. E. M.; Ramonet, M.; Meijer, H. A. J.

    2014-11-01

    We present atmospheric CO2 and δ(O2/N2) from flask samples taken on board aircraft over Fyodorovskoye (56°27‧N, 32°55‧E) at heights of 3000 m and 100 m between 1998 and 2008. The long-term trends for CO2 and δ(O2/N2) are similar for both sampling heights, and also similar to observations from marine background station Mace Head (Ireland) and coastal station Lutjewad (the Netherlands). The seasonal CO2 amplitude at 100 m was almost twice as large as at 3000 m and a phase shift in the seasonality of about two weeks between both sampling heights was observed. This indicates a dominant influence on CO2 in the boundary layer from the regional biosphere which is confirmed by analysis of the δ(O2/N2) to CO2 oxidative ratio (OR). Together with simulations with the TM3 model, our data suggest that the observed OR of -1.7 ± 0.2 in the free troposphere is mainly driven by exchange processes with the ocean. Within the boundary layer an OR of -0.89 ± 0.12 was observed which supports the results of other recent studies suggesting the commonly used value of -1.1 for biospheric OR is likely too low.

  4. Aspects of Supercritical Turbulence: Direct Numerical Simulation of O2/H2 and C7H16/N2 Temporal Mixing Layers

    NASA Technical Reports Server (NTRS)

    Bellan, J.; Okongo, N. A.; Harstad, K. G.; Hutt, John (Technical Monitor)

    2002-01-01

    Results from Direct Numerical Simulations of temporal, supercritical mixing layers for two species systems are analyzed to elucidate species-specific turbulence aspects. The two species systems, O2/H2 and C7HG16/N2, have different thermodynamic characteristics; thus, although the simulations are performed at similar reduced pressure (ratio of the pressure to the critical pressure), the former system is dose to mixture ideality and has a relatively high solubility with respect to the latter, which exhibits strong departures from mixture ideality Due to the specified, smaller initial density stratification, the C7H16/N2 layers display higher growth and increased global molecular mixing as well as larger turbulence levels. However, smaller density gradients at the transitional state for the O2/H2 system indicate that on a local basis, the layer exhibits an enhanced mixing, this being attributed to the increased solubility and to mixture ideality. These thermodynamic features are shown to affect the irreversible entropy production (i.e. the dissipation), which is larger for the O2/H2 layer and is primarily concentrated in high density-gradient magnitude regions that are distortions of the initial density stratification boundary. In contrast, the regions of largest dissipation in the C7H16/N2 layer are located in high density-gradient magnitude regions resulting from the mixing of the two fluids.

  5. Oxidation of Flash-Anodized Al-Mg Alloy in Dry Atmospheres of N2, CO2, and O2 and Humid Atmosphere of Ar

    NASA Astrophysics Data System (ADS)

    LaPointe, Kyle; Bao, Sarina; Kvithyld, Anne

    2015-03-01

    Production of anodized Al alloy is increasing with increased recycling of Al. To study recycling of anodized material, a flash-anodized 3000 series Al alloy containing 0.34 wt pct Mg was remelted in pure atmospheres of CO2, O2, and N2, and Ar with 5 mol pct H2O at 1073 K (800 °C). Hopefully, the results should be of general influence concerning dross formation and scrap remelting in the Al industry. Oxidation studies using a thermogravimetric analyser were performed. Following the treatment, the samples oxide layers were characterized. The highest oxidation rates were observed in atmospheres of O2 and CO2. However, the onset of a break-away oxidation period in O2 is delayed in comparison to CO2. Oxidation in CO2 showed substantially less MgO formation compared to O2. The main source of mass gain can be attributed to the reaction of Mg with oxygen to form MgO and MgAl x O y . Heating in N2 resulted in the lowest mass gain of all atmospheres. Experiments in humid (5 mol pct H2O) Ar atmospheres indicate that there is a minimum threshold of Mg activity to initiate oxidation via H2O. Oxidation kinetics (mechanisms) has been investigated.

  6. Oxidation of melatonin by singlet molecular oxygen (O2(1deltag)) produces N1-acetyl-N2-formyl-5-methoxykynurenine.

    PubMed

    de Almeida, Eduardo A; Martinez, Glaucia R; Klitzke, Clécio F; de Medeiros, Marisa H G; Di Mascio, Paolo

    2003-09-01

    It has been shown that melatonin exhibits antioxidant properties. Chemical structures of some of the products formed by the interaction of melatonin with reactive oxygen and nitrogen species have been elucidated. Despite some evidence that the reaction of melatonin with singlet molecular oxygen (O2(1deltag)) produces N1-acetyl-N2-formyl-5-methoxykynurenine (AFMK), it has not been fully documented. In this investigation, melatonin was oxidized by photosensitization with methylene blue or by a clean chemical source of O2(1deltag), the thermodecomposition of N,N'-di(2,3-dihydroxypropyl)-1,4-naphtalenedipropanamide (DHPNO2). The resulting product was characterized by high performance liquid chromatography, coupled to electrospray ionization mass spectrometry and also by 1H, 13C and dept135 nuclear magnetic resonance spectroscopy. An isotopically labeled DHPN18O2 was also prepared and used as a chemical source of labeled 18[O2(1deltag)] to unequivocally characterize the end product. The results uncovered by this work confirm the hypothesis that oxidation of melatonin by O2(1deltag) produces AFMK.

  7. MCNTs@MnO2 Nanocomposite Cathode Integrated with Soluble O2-Carrier Co-salen in Electrolyte for High-Performance Li-Air Batteries.

    PubMed

    Hu, Xiaofei; Wang, Jianbin; Li, Zifan; Wang, Jiaqi; Gregory, Duncan H; Chen, Jun

    2017-03-08

    Li-air batteries (LABs) are promising because of their high energy density. However, LABs are troubled by large electrochemical polarization during discharge and charge, side reactions from both carbon cathode surface/peroxide product and electrolyte/superoxide intermediate, as well as the requirement for pure O2. Here we report the solution using multiwall carbon nanotubes (MCNTs)@MnO2 nanocomposite cathode integrated with N,N'-bis(salicylidene)ethylenediaminocobalt(II) (Co(II)-salen) in electrolyte for LABs. The advantage of such a combination is that on one hand, the coating layer of δ-MnO2 with about 2-3 nm on MCNTs@MnO2 nanocomposite catalyzes Li2O2 decomposition during charge and suppresses side reactions between product Li2O2 and MCNT surface. On the other hand, Co(II)-salen works as a mobile O2-carrier and accelerates Li2O2 formation through the reaciton of (Co(III)-salen)2-O2(2-) + 2Li(+) + 2e(-) → 2Co(II)-salen + Li2O2. This reaction route overcomes the pure O2 limitation and avoids the formation of aggressive superoxide intermediate (O2(-) or LiO2), which easily attacks organic electrolyte. By using this double-catalyst system of Co-salen/MCNTs@MnO2, the lifetime of LABs is prolonged to 300 cycles at 500 mA g(-1) (0.15 mA cm(-2)) with fixed capacity of 1000 mAh g(-1) (0.30 mAh cm(-2)) in dry air (21% O2). Furthermore, we up-scale the capacity to 500 mAh (5.2 mAh cm(-2)) in pouch-type batteries (∼4 g, 325 Wh kg(-1)). This study should pave a new way for the design and construction of practical LABs.

  8. Prevalence of Bimolecular Routes in the Activation of Diatomic Molecules with Strong Chemical Bonds (O2, NO, CO, N2) on Catalytic Surfaces.

    PubMed

    Hibbitts, David; Iglesia, Enrique

    2015-05-19

    Dissociation of the strong bonds in O2, NO, CO, and N2 often involves large activation barriers on low-index planes of metal particles used as catalysts. These kinetic hurdles reflect the noble nature of some metals (O2 activation on Au), the high coverages of co-reactants (O2 activation during CO oxidation on Pt), or the strength of the chemical bonds (NO on Pt, CO and N2 on Ru). High barriers for direct dissociations from density functional theory (DFT) have led to a consensus that "defects", consisting of low-coordination exposed atoms, are required to cleave such bonds, as calculated by theory and experiments for model surfaces at low coverages. Such sites, however, bind intermediates strongly, rendering them unreactive at the high coverages prevalent during catalysis. Such site requirements are also at odds with turnover rates that often depend weakly on cluster size or are actually higher on larger clusters, even though defects, such as corners and edges, are most abundant on small clusters. This Account illustrates how these apparent inconsistencies are resolved through activations of strong bonds assisted by co-adsorbates on crowded low-index surfaces. Catalytic oxidations occur on Au clusters at low temperatures in spite of large activation barriers for O2 dissociation on Au(111) surfaces, leading to proposals that O2 activation requires low-coordination Au atoms or Au-support interfaces. When H2O is present, however, O2 dissociation proceeds with low barriers on Au(111) because chemisorbed peroxides (*OOH* and *HOOH*) form and weaken O-O bonds before cleavage, thus allowing activation on low-index planes. DFT-derived O2 dissociation barriers are much lower on bare Pt surfaces, but such surfaces are nearly saturated with CO* during CO oxidation. A dearth of vacant sites causes O2* to react with CO* to form *OOCO* intermediates that undergo O-O cleavage. NO-H2 reactions occur on Pt clusters saturated with NO* and H*; direct NO* dissociation requires vacant

  9. Tree Growth-Hybrid Genetic Algorithm for Predicting the Structure of Small (TiO2)n, n = 2-13, Nanoclusters.

    PubMed

    Chen, Mingyang; Dixon, David A

    2013-07-09

    The initial structures for the search for the global minimum of TiO2 nanoclusters were generated by combining a tree growth (TG) algorithm with a hybrid genetic algorithm (HGA). In the TG algorithm, the clusters grow from a small seed to the size of interest stepwise. New atoms are added to the smaller cluster from the previous step, by analogy to new leaves grown by a tree. The addition of the new atoms is controlled by predefined geometry parameters to reduce the computational cost and to provide physically meaningful structures. In each step, the energies for the various generated structures are evaluated, and those with the lowest energies are carried into the next step. The structures that match the formulas of interest are collected as HGA candidates during the various steps. Low energy candidates are fed to the HGA component to search for the global minimum for each formula of interest. The lowest energy structures from the HGA are then optimized by using density functional theory to study the dissociation energies of the clusters and the evolution in the structure as the size of the cluster increases. The optimized geometries of the (TiO2)n nanoclusters for n = 2-13, do not show the character of a TiO2 bulk crystal with a hexacoordinate Ti. The average clustering energy ⟨ΔEn⟩ converges slowly to the bulk value for rutile. The TiO2 dissociation energies for (TiO2)n clusters approach the bulk value for rutile more quickly but show larger variations. The (TiO2)12 cluster appears to be quite stable, and the (TiO2)13 cluster is quite unstable on a relative scale.

  10. Characterization of nanocrystalline nitrogen-containing titanium oxide obtained by N2/O2/Ar low-field helicon plasma sputtering

    NASA Astrophysics Data System (ADS)

    Sarra-Bournet, C.; Haberl, B.; Charles, C.; Boswell, R.

    2011-11-01

    TiO2 and nitrogen-containing TiO2 thin films were deposited on glass and silicon wafer substrates using a helicon-assisted reactive plasma sputtering process in a gas mixture of Ar/O2/N2. The growth mechanism, chemical composition and crystalline structure were probed by x-ray photoelectron spectroscopy, x-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy. The presence of nitrogen in the film induces the formation of some Ti3+ defects states, which introduces oxygen vacancies in the TiOxNy structure. It is also observed that nitrogen substitution selectively hinders the formation of the crystalline rutile phase and promotes the growth of a polycrystalline anatase phase film. Moreover, the film exhibits a red-shift in light absorption from UV to visible spectrum as a function of the nitrogen doping. This work shows that crystalline TiO2 thin films can be obtained with a low temperature process and also shows that using nitrogen can control the desired crystalline structure.

  11. Ab initio molecular dynamics determination of competitive O2 vs. N2 adsorption at open metal sites of M2 (dobdc)

    DOE PAGES

    Parkes, Marie V.; Greathouse, Jeffery A.; Hart, David B.; ...

    2016-04-04

    The separation of oxygen from nitrogen using metal–organic frameworks (MOFs) is of great interest for potential pressure-swing adsorption processes for the generation of purified O2 on industrial scales. This study uses ab initio molecular dynamics (AIMD) simulations to examine for the first time the pure-gas and competitive gas adsorption of O2 and N2 in the M2(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. Lastly, this unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize the process of multiple guestsmore » competitively binding to coordinatively unsaturated metal sites of a MOF.« less

  12. New insulinomimetic zinc(II) complexes of alpha-amino acids and their derivatives with Zn(N2O2) coordination mode.

    PubMed

    Yoshikawa, Y; Ueda, E; Suzuki, Y; Yanagihara, N; Sakurai, H; Kojima, Y

    2001-05-01

    Zinc(II) complexes of alpha-amino acids and their derivatives with a Zn(N2O2) coordination mode were found to have in vitro insulinomimetic activity as estimated with the inhibition of free fatty acid release in isolated rat adipocytes treated with epinephrine. It was revealed that the insulinomimetic activities of zinc(II) complexes with over-all stability constants (log beta) less than 10.5 are higher than those of ZnSO4 and VOSO4. The high blood glucose level of KK-Ay mice with type 2 diabetes mellitus was lowered by daily intraperitoneal injections of a zinc(II) complex, cis-[Zn(L-Thr)2(H2O)2], for 14 d. The improvement of diabetes mellitus was confirmed with the oral glucose tolerance test.

  13. The α and γ plasma modes in plasma-enhanced atomic layer deposition with O2N2 capacitive discharges

    NASA Astrophysics Data System (ADS)

    Napari, M.; Tarvainen, O.; Kinnunen, S.; Arstila, K.; Julin, J.; Fjellvåg, Ø. S.; Weibye, K.; Nilsen, O.; Sajavaara, T.

    2017-03-01

    Two distinguishable plasma modes in the O2N2 radio frequency capacitively coupled plasma (CCP) used in remote plasma-enhanced atomic layer deposition (PEALD) were observed. Optical emission spectroscopy and spectra interpretation with rate coefficient analysis of the relevant processes were used to connect the detected modes to the α and γ modes of the CCP discharge. To investigate the effect of the plasma modes on the PEALD film growth, ZnO and TiO2 films were deposited using both modes and compared to the films deposited using direct plasma. The growth rate, thickness uniformity, elemental composition, and crystallinity of the films were found to correlate with the deposition mode. In remote CCP operations the transition to the γ mode can result in a parasitic discharge leading to uncontrollable film growth and thus limit the operation parameters of the capacitive discharge in the PEALD applications.

  14. Parity-dependent rotational energy transfer in CN(A(2)Π, ν = 4, j F(1)ε) + N2, O2, and CO2 collisions.

    PubMed

    McGurk, Stephen J; Halpern, Joshua B; McKendrick, Kenneth G; Costen, Matthew L

    2014-03-20

    We report state-resolved total removal cross sections and state-to-state rotational energy transfer (RET) cross sections for collisions of CN(A(2)Π, ν = 4, j F1ε) with N2, O2, and CO2. CN(X(2)Σ(+)) was produced by 266 nm photolysis of ICN in a thermal bath (296 K) of the collider gas. A circularly polarized pulse from a dye laser prepared CN(A(2)Π, ν = 4) in a range of F1e rotational states, j = 2.5, 3.5, 6.5, 11.5, 13.5, and 18.5. These prepared states were monitored using the circularly polarized output of an external cavity diode laser by frequency-modulated (FM) spectroscopy on the CN(A-X)(4,2) band. The FM Doppler profiles were analyzed as a function of pump-probe delay to determine the time dependence of the population of the initially prepared states. Kinetic analysis of the resulting time dependences was used to determine total removal cross sections from the initially prepared levels. In addition, a range of j' F1e and j' F2f product states resulting from rotational energy transfer out of the j = 6.5 F1e initial state were probed, from which state-to-state RET cross sections were measured. The total removal cross sections lie in the order CO2 > N2 > O2, with evidence for substantial cross sections for electronic and/or reactive quenching of CN(A, ν = 4) to unobserved products with CO2 and O2. This is supported by the magnitude of the state-to-state RET cross sections, where a deficit of transferred population is apparent for CO2 and O2. A strong propensity for conservation of rotational parity in RET is observed for all three colliders. Spin-orbit-changing cross sections are approximately half of those of the respective conserving cross sections. These results are in marked disagreement with previous experimental observations with N2 as a collider but are in good agreement with quantum scattering calculations from the same study ( Khachatrian et al. J. Phys. Chem. A 2009 , 113 , 3922 ). Our results with CO2 as a collider are similarly in strong

  15. Investigation of the liquid/vapor composition of compressed liquid CO2 with N2 and O2 in integrated pollutant removal systems for coal combustion

    SciTech Connect

    Oryshchyn, Danylo B.; Ochs, Thomas L.; Summers, Cathy A.; Penner, Larry R.; Gerdemann, Stephen J.

    2005-01-01

    Accurate prediction of the processes in Integrated Pollutant Removal (IPR) using compression and condensation of coal combustion products requires an understanding of the liquid/vapor ternary CO2/O2/N2 system. At conditions close to the critical point of CO2 the existing equations of state deviate from the sparse measured results available in the literature. Building on existing data and procedures, the USDOE/Albany Research Center has designed an apparatus for examining compositions in this region. The design of the apparatus and planned initial experiments are presented.

  16. Sterilization/disinfection of medical devices using plasma: the flowing afterglow of the reduced-pressure N2-O2 discharge as the inactivating medium

    NASA Astrophysics Data System (ADS)

    Moisan, Michel; Boudam, Karim; Carignan, Denis; Kéroack, Danielle; Levif, Pierre; Barbeau, Jean; Séguin, Jacynthe; Kutasi, Kinga; Elmoualij, Benaïssa; Thellin, Olivier; Zorzi, Willy

    2013-07-01

    Potential sterilization/disinfection of medical devices (MDs) is investigated using a specific plasma process developed at the Université de Montréal over the last decade. The inactivating medium of the microorganisms is the flowing afterglow of a reduced-pressure N2-O2 discharge, which provides, as the main biocidal agent, photons over a broad ultraviolet (UV) wavelength range. The flowing afterglow is considered less damaging to MDs than the discharge itself. Working at gas pressures in the 400—700 Pa range (a few torr) ensures, through species diffusion, the uniform filling of large volume chambers with the species outflowing from the discharge, possibly allowing batch processing within them. As a rule, bacterial endospores are used as bio-indicators (BI) to validate sterilization processes. Under the present operating conditions, Bacillus atrophaeus is found to be the most resistant one and is therefore utilized as BI. The current paper reviews the main experimental results concerning the operation and characterization of this sterilizer/disinfector, updating and completing some of our previously published papers. It uses modeling results as guidelines, which are particularly useful when the corresponding experimental data are not (yet) available, hopefully leading to more insight into this plasma afterglow system. The species flowing out of the N2-O2 discharge can be divided into two groups, depending on the time elapsed after they left the discharge zone as they move toward the chamber, namely the early afterglow and the late afterglow. The early flowing afterglow from a pure N2 discharge (also called pink afterglow) is known to be comprised of N2+ and N4+ ions. In the present N2-O2 mixture discharge, NO+ ions are additionally generated, with a lifetime that extends over a longer period than that of the nitrogen molecular ions. We shall suppose that the disappearance of the NO+ ions marks the end of the early afterglow regime, thereby stressing our intent

  17. Prediction of the temperature dependence of the surface tension of SO2, N2, O2, and Ar by Monte Carlo molecular simulations.

    PubMed

    Neyt, Jean-Claude; Wender, Aurélie; Lachet, Véronique; Malfreyt, Patrice

    2011-08-04

    We report Monte Carlo simulations of the liquid-vapor interface of SO(2), O(2), N(2), and Ar to reproduce the dependence of the surface tension with the temperature. Whereas the coexisting densities, critical temperature, density, and pressure are very well reproduced by the two-phase simulations showing the same accuracy as the calculations performed using the Gibbs ensemble Monte Carlo technique (GEMC), the performance of the prediction of the variation of the surface tension with the temperature depends on the magnitude of the electrostatic and repulsive-dispersive interactions. The surface tension of SO(2) is very well reproduced, whereas the prediction of this property is less satisfactory for O(2) and N(2), for which the average intermolecular electrostatic interactions are several orders smaller than the dispersion interactions. For argon, we observe significant deviations from experiments. The representation of the surface tension of argon in reduced units shows that our calculations are in line with the existing surface tensions of the Lennard-Jones fluid in the literature. This underlines the difficulty of reproducing the temperature dependence of the surface tension of argon with interactions only modeled by the Lennard-Jones pair potential.

  18. The role of the long-range tail of the potential in O2 + N2 collisional inelastic vibrational energy transfers.

    PubMed

    Garcia, Ernesto; Pirani, Fernando; Laganà, Antonio; Martí, Carles

    2017-05-10

    In the study of non-reactive energy transfer between O2 and N2 molecules bearing different vibrationally excited states we have faced the problem of selecting a proper formulation of the interaction. To this end we have compared the values of the related observables computed either on a potential energy surface globally fitted to very large ab initio potential energy values [Varga et al., J. Chem. Phys., 2016, 144, 024310] or on two more traditional ones formulated as a combination of an intra- and inter-molecular model component of the interaction (and based on a different combined use of experimental and ab initio information) [Garcia et al., J. Phys. Chem. A, 2016, 120, 5208] in order to enforce an appropriate modelling of the long-range tail of the potential, crucial for the description of inelastic vibrational energy transfer. A detailed graphical analysis of the potential plus a quantitative analysis of the computed opacity functions, of the state-to-state rate coefficients, of the second virial coefficient and of the integral non-reactive cross section allowed us to conclude that the model formulation of the interaction has to be preferred for non-reactive studies of the O2 + N2 energy transfer processes in thermal and subthermal regimes.

  19. Study of OH radical generation in atmospheric pressure microwave plasma jets of Ar, N2 and O2 gases using pulsed cavity ringdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Chuji; Srivastava, Nimisha

    2009-11-01

    We employ UV-pulsed laser cavity ringdown spectroscopy, optical emission spectroscopy and visual imaging, to characterize OH radical generation in atmospheric pressure microwave plasma jets created, respectively, by argon, mixture of Ar and N2, mixture of Ar and O2, and mixture of Ar, N2 and O2. OH radicals were observed in far downstream for all of these plasma jets (Far downstream is referred to as the location where ratio of the distance from the jet orifice to the length of the jet column is > 3).We also investigated the effect of variations in humidity on OH generation in the APJs. Absolute number densities were measured for OH (v'' = 0, J''= 3.5) along the plasma column axis. Effects on OH radical concentrations along the plasma column axis with variations of plasma powers, gas flow rates with different mixing ratios and humidity levels were also studied. The rotational Trot, vibrational Tvib and electronic excitation temperature Telex were provided by simulations of emission spectra of the plasmas.

  20. Studies via Near-Infrared Cavity Ringdown Spectroscopy and Electronic Structure Calculations of the Products of the Photolysis of Dihalomethane/N2/O2 Mixtures.

    PubMed

    Huang, Meng; Kline, Neal; Miller, Terry A; Dawes, Richard

    2017-01-12

    Near-infrared cavity ringdown spectra were recorded following the photolysis of dihalomethanes in O2/N2 mixtures. In particular, photolysis of CH2I2 under conditions previously reported to produce the simplest Criegee intermediate, CH2O2, gave a complex, structured spectrum between 6800 and 9000 cm(-1), where the lowest triplet-singlet transition (ã-X̃) of CH2O2 might be expected. To help identify the carrier of the spectrum, extensive electronic structure calculations were performed on the ã and X̃ states of CH2O2 and the lowest two doublet states of the iodomethylperoxy radical, CH2IO2, which also could be produced by the chemistry and whose Ã-X̃ transition likely lies in this spectral region. The conclusion of these calculations is that the ã-X̃ transition of CH2O2 clearly falls outside the observed spectral range and would be extremely weak both because it is spin-forbidden and because of a large geometric change between the ã and X̃ states. Moreover, only a shallow well (with a barrier to dissociation of less than 1900 cm(-1)) is predicted on the ã state, which likely precludes the existence of long-lived states. Calculations for the Ã-X̃ transition of CH2IO2 are generally consistent with the observed spectrum in terms of both the electronic origin and vibrational frequencies in the à state. To confirm the carrier assignment to CH2IO2, calculations beyond the Franck-Condon approximation were carried out to explain the hot band structure of the large-amplitude, low-frequency O-O-C-I torsion mode, ν12. Photolysis of other dihalomethanes produced similar spectra which were analyzed and assigned to CH2ClO2 and CH2BrO2. Experimental values for the electronic energies and frequencies for several à state vibrations and the ν12 vibration of the X̃ state of each are reported. In addition, the observed spectra were used to follow the self-reaction of the CH2IO2 species and its reaction with SO2. The rates of these reactions are dramatically faster than

  1. Theoretical Investigation of Methane Hydroxylation over Isoelectronic [FeO](2+)- and [MnO](+)-Exchanged Zeolites Activated by N2O.

    PubMed

    Mahyuddin, M Haris; Shiota, Yoshihito; Staykov, Aleksandar; Yoshizawa, Kazunari

    2017-09-05

    While the most likely structure of the active site in iron-containing zeolites has been recently identified as [FeO](2+) (Snyder et al. Nature 2016, 536, 317-321), the mechanism for the direct conversion of methane to methanol over this active species is still debatable between the direct-radical-rebound or nonradical (concerted) mechanism. Using density functional theory on periodic systems, we calculated the two reaction mechanisms over two d(4) isoelectronic systems, [FeO](2+) and [MnO](+) zeolites. We found that [FeO](2+) zeolites favor the direct-radical-rebound mechanism with low CH4 activation energies, while [MnO](+) zeolites prefer the nonradical mechanism with higher CH4 activation energies. These contrasts, despite their isoelectronic structures, are mainly due to the differences in the metal coordination number and Oα (oxo) spin density. Moreover, molecular orbital analyses suggest that the zeolite steric hindrance further degrades the reactivity of [MnO](+) zeolites toward methane. Two types of zeolite frameworks, i.e., medium-pore ZSM-5 (MFI framework) and small-pore SSZ-39 (AEI framework) zeolites, were evaluated, but no significant differences in the reactivity were found. The rate-determining reaction step is found to be methanol desorption instead of methane activation. Careful examination of the most stable sites hosting the active species and calculation for N2O decomposition over [Fe](2+)-MFI and -AEI zeolites were also performed.

  2. Nickel(II) in chelate N2O2 environment. DFT approach and in-depth molecular orbital and configurational analysis.

    PubMed

    Trifunović, Srećko R; Miletić, Vesna D; Jevtić, Verica V; Meetsma, Auke; Matović, Zoran D

    2013-10-07

    The O-N-N-O-type tetradentate ligands H2S,S-eddp (H2S,S-eddp stands for S,S-ethylenediamine-N,N'-di-2-propionic acid) and H2edap (H2edap stands for ethylenediamine-N-acetic-N'-3-propionic acid) and the corresponding novel octahedral nickel(II) complexes have been prepared and characterized. N2O2 ligands coordinate to the nickel(II) ion via four donor atoms (two deprotonated carboxylate atoms and two amine nitrogens) affording octahedral geometry in the case of all investigated Ni(II) complexes. A six coordinate, octahedral geometry has been verified crystallographically for the s-cis-[Ni(S,S-eddp)(H2O)2] complex. Structural data correlating similarly chelated Ni(II) complexes have been used to carry out an extensive configuration analysis. Molecular mechanics and Density Functional Theory (DFT) have been used to model the most stable geometric isomer, yielding, at the same time, significant structural and spectroscopic (TDDFT) data. The results from density functional studies have been compared to X-ray data. Natural Bond Orbital (NBO) and Natural Energetic Decomposition Analysis (NEDA) have been done for the [Ni(edda-type)(H2O)(2-n)] and nH2O fragments. Molecular orbital analysis (MPA) is given as well. The infra-red and electronic absorption spectra of the complexes are discussed in comparison to the related complexes of known geometries.

  3. Oxidation of atomic gold ions: thermochemistry for the activation of O(2) and N(2)O BY Au(+) ((1)S(0) and (3)D).

    PubMed

    Li, Feng-Xia; Gorham, Katrine; Armentrout, P B

    2010-10-28

    Reaction of Au(+) ((1)S(0) and (3)D) with O(2) and N(2)O is studied as a function of kinetic energy using guided ion beam tandem mass spectrometry. A flow tube ion source produces Au(+) primarily in its (1)S(0) (5d(10)) electronic ground state level but with some (3)D and perhaps higher lying excited states. The distribution of states can be altered by adding N(2)O, which completely quenches the excited states, or CH(4) to the flow gases. Cross sections as a function of kinetic energy are measured for both neutral reagents and both ground and excited states of Au(+). Formation of AuO(+) is common to both systems with the N(2)O system also exhibiting AuN(2)(+) and AuNO(+) formation. All reactions of Au(+) ((1)S(0)) are observed to be endothermic, whereas the excitation energy available to the (3)D state allows some reactions to be exothermic. Because of the closed shell character of ground state Au(+) ((1)S(0), 5d(10)), the reactivity of these systems is low and has cross sections with onsets and peaks at higher energies than expected from the known thermochemistry but lower than energies expected from impulsive processes. Analyses of the endothermic reaction cross sections yield the 0 K bond dissociation energy (BDE) in eV of D(0)(Au(+)-O) = 1.12 ± 0.08, D(0)(Au(+)-N(2)) ≥ 0.30 ± 0.04, and D(0)(Au(+)-NO) = 0.89 ± 0.17, values that are all speculative because of the unusual experimental behavior. Combining the AuO(+) BDE measured here with literature data also yields the ionization energy of AuO as 10.38 ± 0.23 eV. Quantum chemical calculations show reasonable agreement with the experimental bond energies and provide the electronic structures of these species.

  4. Constraining N2O emissions since 1940 by firn air isotope measurements in both hemispheres

    NASA Astrophysics Data System (ADS)

    Prokopiou, Markella; Martinerie, Patricia; Sapart, Celia; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Kaiser, Jan; Levin, Ingeborg; Sowers, Todd; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik; Röckmann, Thomas

    2017-04-01

    N2O is currently the 3rd most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290±1) nmol mol-1 in 1940 to (322±1) nmol mol-1 in 2008 the isotopic δ values of atmospheric N2O decreased by (- 2.2±0.2) ‰ for δ15Nav, (- 1.0±0.3) ‰ for δ18O, (- 1.3±0.6) ‰ for δ15Nα, and (- 2.8±0.6) ‰ for δ15Nβover the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to be 123 a. Adopting this lifetime results in total average source isotopic signatures of (- 7.6±0.8) ‰ (vs. Air-N2) for δ15Nav, (32.2±0.2) ‰ (vs. VSMOW) for δ18O, (- 3.0±1.9) ‰ (vs. Air-N2) for δ15Nα, and (- 11.7±2.3) ‰ (vs. Air-N2) for δ15Nβ over the investigated period. δ15Navand δ15Nβ show some temporal variability while the other source isotopic signatures remain unchanged. The 15N site-preference (= δ15Nα - δ15Nβ) can be used to reveal further information on the source emission origins. Based on the changes in the isotopes we conclude that the main contribution to N2O changes in the atmosphere since 1940 is from soils, with agricultural soils being the principal anthropogenic component, which is in line with previous studies.

  5. Investigation on the Charging Process of Li2O2-Based Air Electrodes in Li-O2 Batteries with Organic Carbonate Electrolytes

    SciTech Connect

    Xu, Wu; Viswanathan, Vilayanur V.; Wang, Deyu; Towne, Silas A.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Zhang, Jiguang

    2011-04-15

    The charge processes of Li-O2 batteries were investigated by analyzing the gas evolution by in situ gas chromatography-mass spectroscopy (GC/MS) technique. The mixture of Li2O2/Fe3O4/Super P carbon/polyvinylidene fluoride (PVDF) was used as the starting air electrode material and 1M LiTFSI in carbonate-based solvents was used as electrolyte. It was found that Li2O2 is reactive to 1-methyl-2-pyrrolidinone and PVDF binder used in the electrode preparation. During the 1st charge (up to 4.6 V), O2 was the main component in the gases released. The amount of O2 measured by GC/MS was consistent with the amount of Li2O2 decomposed in the electrochemical process as measured by the charge capacity, indicative of the good chargeability of Li2O2. However, after the cell was discharged to 2.0 V in O2 atmosphere and re-charged to ~ 4.6 V in the second cycle, CO2 was dominant in the released gases. Further analysis of the discharged air electrode by X-ray diffraction and Fourier transform infrared spectroscopy indicated that lithium-containing carbonate species (lithium alkyl carbonate and/or Li2CO3) were the main reaction products. Therefore, compatible electrolyte and electrodes as well as the electrode preparation procedures need to be developed for long term operation of rechargeable Li-O2 or Li-air batteries.

  6. Stabilizing MoS2 Nanosheets through SnO2 Nanocrystal Decoration for High-Performance Gas Sensing in Air.

    PubMed

    Cui, Shumao; Wen, Zhenhai; Huang, Xingkang; Chang, Jingbo; Chen, Junhong

    2015-05-20

    The unique properties of MoS(2) nanosheets make them a promising candidate for high-performance room temperature sensing. However, the properties of pristine MoS(2) nanosheets are strongly influenced by the significant adsorption of oxygen in an air environment, which leads to instability of the MoS(2) sensing device, and all sensing results on MoS(2) reported to date were exclusively obtained in an inert atmosphere. This significantly limits the practical sensor application of MoS(2) in an air environment. Herein, a novel nanohybrid of SnO(2) nanocrystal (NC)-decorated crumpled MoS(2) nanosheet (MoS(2)/SnO(2)) and its exciting air-stable property for room temperature sensing of NO(2) are reported. Interestingly, the SnO(2) NCs serve as strong p-type dopants for MoS(2), leading to p-type channels in the MoS(2) nanosheets. The SnO(2) NCs also significantly enhance the stability of MoS(2) nanosheets in dry air. As a result, unlike other MoS(2) sensors operated in an inert gas (e.g. N(2)), the nanohybrids exhibit high sensitivity, excellent selectivity, and repeatability to NO(2) under a practical dry air environment. This work suggests that NC decoration significantly tunes the properties of MoS(2) nanosheets for various applications.

  7. Vibrational relaxation of H2O(|04> ) in collisions with H2O, Ar, H2, N2 and O2: dynamical and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Barnes, P. W.; Sims, I. R.; Smith, I. W.

    2003-04-01

    It has been suggested that sequential two-photon dissociation of water might provide a mechanism for the atmospheric production of OH radical. ^1 This mechanism requires that photodissociation of vibrationally excited molecules must occur at a rate competitive with their relaxation by collisions with atmospheric gases. In this paper, we shall describe new experiments on the collisional relaxation of H_2O molecules from the highly excited mid04>± vibrational state in collisions with H_2O, Ar, H_2, N_2 and O_2. In our experiments, the mid04>^- state is populated by direct absorption of radiation from a pulsed dye laser tuned to ca. 719 nm. Evolution of the population in the (mid04>±) levels is observed using the combination of a frequency-quadrupled Nd:YAG laser, which selectively photolyses H_2O(mid04>±), and a frequency-doubled dye laser, which observes the OH(v = 0) produced via laser-induced fluorescence (LIF). The delay between the pulse from the pump laser and those from the photolysis and probe lasers was systematically varied to generate kinetic decays. The rate coefficients for relaxation obtained from these experiments, in units of cm^3 molecule-1 s-1, are: k(H_2O) = (4.1 ± 1.2) x 10-10, k(Ar) = (4.9 ± 1.1) x 10-12, k(H_2) = (6.8 ± 1.1) x 10-12, k(N_2) = (7.7 ± 1.5) x 10-12, k(O_2) = (6.7 ± 1.4) x 10-12. The results will be discussed in two contexts. First, we shall consider the implications of our new results for the interpretation of our previous experiments on the reactions of vibrationally excited H_2O with H atoms.^2 Second, we shall consider the proposal of Goss et al.1 in the light of our finding that the collisional relaxation of H_2O(mid04>±) by N_2 and O_2 is rather rapid. ^1 L. M Goss, V. Vaida, J. W. Brault and R. T. Skodje, J. Phys. Chem. A, 05, 70 (2001). ^2 (a) G. Hawthorne, P. Sharkey and I. W. M. Smith, J. Chem. Phys., 108, 4693(1998); (b) P. W. Barnes, P. Sharkey, I. R. Sims and I. W. M. Smith, Faraday Discuss. Chem. Soc., 13, 167

  8. Solvatochromism, spectral properties and antimicrobial activities of new azo-azomethine dyes with N2S2O2 donor set of atoms

    NASA Astrophysics Data System (ADS)

    Khanmohammadi, Hamid; Pass, Maryam; Rezaeian, Khatereh; Talei, Gholamreza

    2014-08-01

    Six new azo-azomethine dyes, H2Ln (n = 1-6), with N2S2O2 donor set of atoms have been prepared via condensation reaction of 1,10-diaza-4,7-dithiadecane, I, with substituted azo-coupled salicylaldehyde. The dyes were characterized by IR, UV-Vis and 1H NMR spectroscopic methods as well as elemental analysis. The solvatochromic behavior of the dyes was also probed by studying their UV-Vis spectra in four pure organic solvents of different polarities and a meaningful correlation was observed. Furthermore, all prepared dyes were assayed for their antibacterial and antifungal activities by disc diffusion method. The results indicated that all prepared dyes show good inhibition against Staphylococcus epidermidis and Bacillus cereus and did not show any antibacterial activity against Escherichia coli as compared to standard drugs.

  9. Transferable force-field for modelling of CO2, N2, O2 and Ar in all silica and Na+ exchanged zeolites

    NASA Astrophysics Data System (ADS)

    Vujić, Bojan; Lyubartsev, Alexander P.

    2016-05-01

    In this work we propose a new force field for modelling of adsorption of CO2, N2, O2 and Ar in all silica and Na+ exchanged Si-Al zeolites. The force field has a standard molecular-mechanical functional form with electrostatic and Lennard-Jones interactions satisfying Lorentz-Berthelot mixing rules and thus has a potential for further extension in terms of new molecular types. The parameters for the zeolite framework atom types are optimized by an iterative procedure minimizing the difference with experimental adsorption data for a number of different zeolite structures and Si:Al ratios. The new force field shows a good agreement with available experimental data including those not used in the optimization procedure, and which also shows a reasonable transferability within different zeolite topologies. We suggest a potential usage in screening of different zeolite structures for carbon capture and storage process, and more generally, for separation of other gases.

  10. Mass spectrometry of diffuse coplanar surface barrier discharge: influence of discharge frequency and oxygen content in N2/O2 mixture*

    NASA Astrophysics Data System (ADS)

    Čech, Jan; Brablec, Antonín; Černák, Mirko; Puač, Nevena; Selaković, Nenad; Petrović, Zoran Lj.

    2017-02-01

    Diffuse Coplanar Surface Barrier Discharge (DCSBD) has been studied extensively for industrial applications in recent decade. So far, limited information was available on the production of ozone or nitrogen oxides important for industrial deployment of DCSBD. In this paper results of mass spectrometry of DCSBD performed at atmospheric pressure are presented. DCSBD mass spectra were studied for different oxygen contents in N2/O2 working gas mixture at low flow rate (estimated residence time in discharge chamber was approx. 3 s). Influence of the driving frequency (15, 30 and 50 kHz) at constant high voltage amplitude was studied as well. Ozone and NO production in DCSBD are given as typical representatives. Production of ozone decreases with the driving frequency, which could be attributed to the gas heating at higher frequencies.

  11. FAST TRACK COMMUNICATION: On the application of inductively coupled plasma discharges sustained in Ar/O2/N2 ternary mixture for sterilization and decontamination of medical instruments

    NASA Astrophysics Data System (ADS)

    Stapelmann, K.; Kylián, O.; Denis, B.; Rossi, F.

    2008-10-01

    Non-equilibrium low pressure-plasma discharges are extensively studied for their high potential in the field of sterilization and decontamination of medical devices. This increased interest in plasma discharges arises from, among other reasons, their capability not only to inactivate bacterial spores but also to eliminate, destroy or remove pathogenic biomolecules and thus to provide a one-step process assuring safety of treated instruments. However, recent studies have shown that optimal conditions leading to inactivation of spores and physical removal of pathogens differ significantly—the efficiency of spores sterilization is above all dependent on the UV radiation intensity, whereas high etching rates are connected with the presence of the etching agent, typically atomic oxygen. The aim of this contribution is to discuss and demonstrate the feasibility of Ar/N2/O2 low-pressure inductively coupled plasma discharges as an option to provide intense UV radiation while maintaining the high etching rates of biomolecules.

  12. Pressure broadening and collisional narrowing in OH(v=1 <-- 0) rovibrational transitions with Ar, He, O2, and N2

    NASA Astrophysics Data System (ADS)

    Schiffman, A.; Nesbitt, David J.

    1994-02-01

    Line shapes are measured for OH(v=1←0) transitions in the presence of Ar, He, O2, and N2 as a function of N rotational, spin-orbit, and λ doublet states. Pressure broadening coefficients for all transitions and buffer gases are determined from fits of the observed line shapes to the Voigt profile. The dependencies of the observed broadening coefficients on the OH quantum levels are discussed and compared with previous pressure broadening studies in HF and NO. The observed OH line shapes are interpreted in terms of their impact on the determination of mesospheric and stratospheric OH populations, temperatures, and quantum state distributions from OH nightglow and dayglow emission. In the case of OH+Ar, evidence for Dicke narrowing is presented and narrowing coefficients are reported from fits to a ``hard collision'' model.

  13. Parity-Dependent Rotational Energy Transfer in CN(A2Π, ν = 4, jF1ε) + N2, O2, and CO2 Collisions

    PubMed Central

    2015-01-01

    We report state-resolved total removal cross sections and state-to-state rotational energy transfer (RET) cross sections for collisions of CN(A2Π, ν = 4, jF1ε) with N2, O2, and CO2. CN(X2Σ+) was produced by 266 nm photolysis of ICN in a thermal bath (296 K) of the collider gas. A circularly polarized pulse from a dye laser prepared CN(A2Π, ν = 4) in a range of F1e rotational states, j = 2.5, 3.5, 6.5, 11.5, 13.5, and 18.5. These prepared states were monitored using the circularly polarized output of an external cavity diode laser by frequency-modulated (FM) spectroscopy on the CN(A–X)(4,2) band. The FM Doppler profiles were analyzed as a function of pump–probe delay to determine the time dependence of the population of the initially prepared states. Kinetic analysis of the resulting time dependences was used to determine total removal cross sections from the initially prepared levels. In addition, a range of j′ F1e and j′ F2f product states resulting from rotational energy transfer out of the j = 6.5 F1e initial state were probed, from which state-to-state RET cross sections were measured. The total removal cross sections lie in the order CO2 > N2 > O2, with evidence for substantial cross sections for electronic and/or reactive quenching of CN(A, ν = 4) to unobserved products with CO2 and O2. This is supported by the magnitude of the state-to-state RET cross sections, where a deficit of transferred population is apparent for CO2 and O2. A strong propensity for conservation of rotational parity in RET is observed for all three colliders. Spin–orbit-changing cross sections are approximately half of those of the respective conserving cross sections. These results are in marked disagreement with previous experimental observations with N2 as a collider but are in good agreement with quantum scattering calculations from the same study (Khachatrian et al. J. Phys. Chem. A2009, 113, 392219215110). Our results with CO2 as a collider are similarly in strong

  14. Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces

    SciTech Connect

    Smith, R. Scott; May, Robert A.; Kay, Bruce D.

    2016-03-03

    The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from grapheme covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multi- layer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do not align (for coverages < 2 ML). The non-alignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.

  15. Relaxation of H2O from its |04>- vibrational state in collisions with H2O, Ar, H2, N2, and O2

    NASA Astrophysics Data System (ADS)

    Barnes, Peter W.; Sims, Ian R.; Smith, Ian W. M.

    2004-03-01

    We report rate coefficients at 293 K for the collisional relaxation of H2O molecules from the highly excited |04>± vibrational states in collisions with H2O, Ar, H2, N2, and O2. In our experiments, the |04>- state is populated by direct absorption of radiation from a pulsed dye laser tuned to ˜719 nm. Evolution of the population in the (|04>±) levels is observed using the combination of a frequency-quadrupled Nd:YAG laser, which selectively photolyses H2O(|04>±), and a frequency-doubled dye laser, which observes the OH(v=0) produced by photodissociation via laser-induced fluorescence. The delay between the pulse from the pump laser and those from the photolysis and probe lasers was systematically varied to generate kinetic decays. The rate coefficients for relaxation of H2O(|04>±) obtained from these experiments, in units of cm3 molecule-1 s-1, are: k(H2O)=(4.1±1.2)×10-10, k(Ar)=(4.9±1.1)×10-12, k(H2)=(6.8±1.1)×10-12, k(N2)=(7.7±1.5)×10-12, k(O2)=(6.7±1.4)×10-12. The implications of these results for our previous reports of rate constants for the removal of H2O molecules in selected vibrational states by collisions with H atoms (P. W. Barnes et al., Faraday Discuss. Chem. Soc. 113, 167 (1999) and P. W. Barnes et al., J. Chem. Phys. 115, 4586 (2001).) are fully discussed.

  16. Relaxation of H2O from its /04>- vibrational state in collisions with H2O, Ar, H2, N2, and O2.

    PubMed

    Barnes, Peter W; Sims, Ian R; Smith, Ian W M

    2004-03-22

    We report rate coefficients at 293 K for the collisional relaxation of H2O molecules from the highly excited /04>(+/-) vibrational states in collisions with H2O, Ar, H2, N2, and O2. In our experiments, the mid R:04(-) state is populated by direct absorption of radiation from a pulsed dye laser tuned to approximately 719 nm. Evolution of the population in the (/04>(+/-)) levels is observed using the combination of a frequency-quadrupled Nd:YAG laser, which selectively photolyses H2O(/04>(+/-)), and a frequency-doubled dye laser, which observes the OH(v=0) produced by photodissociation via laser-induced fluorescence. The delay between the pulse from the pump laser and those from the photolysis and probe lasers was systematically varied to generate kinetic decays. The rate coefficients for relaxation of H2O(/04>(+/-)) obtained from these experiments, in units of cm3 molecule(-1) s(-1), are: k(H2O)=(4.1+/-1.2) x 10(-10), k(Ar)=(4.9+/-1.1) x 10(-12), k(H2)=(6.8+/-1.1) x 10(-12), k(N2)=(7.7+/-1.5) x 10(-12), k(O2)=(6.7+/-1.4) x 10(-12). The implications of these results for our previous reports of rate constants for the removal of H2O molecules in selected vibrational states by collisions with H atoms (P. W. Barnes et al., Faraday Discuss. Chem. Soc. 113, 167 (1999) and P. W. Barnes et al., J. Chem. Phys. 115, 4586 (2001).) are fully discussed.

  17. Closer versus Long Range Interaction Effects on the Non-Arrhenius Behavior of Quasi-Resonant O2 + N2 Collisions.

    PubMed

    Kurnosov, A; Cacciatore, M; Pirani, F; Laganà, A; Martí, C; Garcia, E

    2017-07-13

    We report in this paper an investigation on energy transfer processes from vibration to vibration and/or translation in thermal and subthermal regimes for the O2 + N2 system performed using quantum-classical calculations on different empirical, semiempirical, and ab initio potential energy surfaces. In particular, the paper focuses on the rationalization of the non-Arrhenius behavior (inversion of the temperature dependence) of the quasi-resonant vibration-to-vibration energy transfer transition rate coefficients at threshold. To better understand the microscopic nature of the involved processes, we pushed the calculations to the detail of the related cross sections and analyzed the impact of the medium and long-range components of the interaction on them. Furthermore, the variation with temperature of the dependence of the quasi-resonant rate coefficient on the vibrational energy gap between initial and final vibrational states and the effectiveness of quantum-classical calculations to overcome the limitations of the purely classical treatments were also investigated. These treatments, handled in an open molecular science fashion by chaining data and competencies of the various laboratories using a grid empowered molecular simulator, have allowed a rationalization of the dependence of the computed rate coefficients in terms of the distortion of the O2-N2 configuration during the diatom-diatom collisions. A way of relating such distortions to a smooth and continuous progress variable, allowing a proper evolution from both long to closer range formulation of the interaction and from its entrance to exit channel (through the strong interaction region) relaxed graphical representations, is also discussed in the paper.

  18. Synthesis, spectral characterization, thermal analysis, molecular modeling and antimicrobial activity of new potentially N2O2 azo-dye Schiff base complexes

    NASA Astrophysics Data System (ADS)

    Alaghaz, Abdel-Nasser M. A.; Ammar, Yousry A.; Bayoumi, Hoda A.; Aldhlmani, Sharah A.

    2014-09-01

    The azo-dye Schiff's base of N2O2 dibasic ligand, H2L [N,N‧-bis(5-(4-sulfanilamidophenylazosalicylidene)ethylenediamine] was prepared by the condensation of ethylenediamine with [5-(4-sulfanilamidophenylazo-salicylaldehyde] in ethanol. New complexes of with metal ions Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Cd(II), Pt(IV), Fe(III) and Cr(III) are synthesized. Elemental, spectroscopic and thermal analyses as well as conductivity and magnetic susceptibility measurements are used to elucidate the structure of the newly prepared metal complexes. The azo-dye Schiff's base behaves as a di-negative N2O2 tetradentate ligand. The metal complexes exhibited square planar, tetrahedral and octahedral geometrical arrangements, the molar conductivity data indicates that all complexes are neutral. The thermogravimetry (TG) and differential thermoanalysis (DTA) of the Cu(II), Mn(II), Cr(III) and Co(II) complexes were carried out in the range of 30-800 °C. The complexes were decomposed in one and two stages of the Cu(II), Mn(II), Cr(III) and Co(II) complexes, respectively. Also, decomposition of the synthesized complexes is related to the Schiff's base characteristics. The thermal decomposition of the studied reactions was first order. The kinetic parameters for the decomposition steps in Cu(II), Mn(II), Cr(III) and Co(II) complexes thermograms have been calculated using Broido's method. In molecular modeling the geometries of azo-dye Schiff base ligand H2L and its metal(II/III/IV) complexes were fully optimized with respect to the energy using the 6-31G basis set. Antimicrobial activities of the azo-dye Schiff's base ligand and its corresponding metal complexes were screened against various organisms. The azo-dye Schiff's base ligand and some of its complexes were found to be biologically inactive.

  19. Impact of Mixture Gas Plasma of N2 and O2 as the N Source on ZnO-Based Ultraviolet Light-Emitting Diodes Fabricated by Molecular Beam Epitaxy

    NASA Astrophysics Data System (ADS)

    Kato, Hiroyuki; Yamamuro, Tomofumi; Ogawa, Akio; Kyotani, Chizu; Sano, Michihiro

    2011-09-01

    ZnO-based double-heterostructure ultraviolet light-emitting diodes (LEDs) were fabricated on n-type Zn-polar ZnO substrates by plasma-assisted molecular beam epitaxy employing mixture gas plasma of N2 and O2 as the N source. By using mixture gas plasma of N2 with a little added O2, the number of N atoms increased and N2 molecules decreased, as confirmed by optical emission spectrometry. The fabricated LEDs had an ultraviolet near-band-emission of around 380 nm. The integrated electroluminescence intensity of the LED fabricated using N2 and O2 plasma was more than 10 times higher than that of an LED fabricated using N2 plasma.

  20. Studies on DNA binding behaviour of biologically active transition metal complexes of new tetradentate N2O2 donor Schiff bases: Inhibitory activity against bacteria

    NASA Astrophysics Data System (ADS)

    Sobha, S.; Mahalakshmi, R.; Raman, N.

    A series of Cu(II), Ni(II) and Zn(II) complexes of the type ML have been synthesized with Schiff bases derived from o-acetoacetotoluidide, 2-hydroxybenzaldehyde and o-phenylenediamine/1,4-diaminobutane. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytic in nature. All the six metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The analytical data helped to elucidate the structure of the metal complexes. The Schiff bases are found to act as tetradentate ligands using N2O2 donor set of atoms leading to a square-planar geometry for the complexes around all the metal ions. The binding properties of metal complexes with DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. Detailed analysis reveals that the metal complexes intercalate into the DNA base stack as intercalators. All the metal complexes cleave the pUC19 DNA in presence of H2O2. The Schiff bases and their complexes have been screened for their antibacterial activity against five bacterial strains (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, Klebsiella pneumoniae) by disk diffusion method. All the metal complexes have potent biocidal activity than the free ligands.

  1. Review of the absorption spectra of solid O2 and N2 as they relate to contamination of a cooled infrared telescope

    NASA Technical Reports Server (NTRS)

    Smith, S. M.

    1977-01-01

    During contamination studies for the liquid helium cooled shuttle infrared telescope facility, a literature search was conducted to determine the absorption spectra of the solid state of homonuclear molecules of O2 and N2, and ascertain what laboratory measurements of the solid have been made in the infrared. With the inclusion of one unpublished spectrum, the absorption spectrum of the solid oxygen molecule has been thoroughly studied from visible to millimeter wavelengths. Only two lines appear in the solid that do not also appear in the gas or liquid. A similar result is implied for the solid nitrogen molecule because it also is homonuclear. The observed infrared absorption lines result from lattice modes of the alpha phase of the solid, and disappear at the warmer temperatures of the beta, gamma, and liquid phases. They are not observed from polycrystalline forms of O2, while strong scattering is. Scattering, rather than absorption, is considered to be the principal natural contamination problem for cooled infrared telescopes in low earth orbit.

  2. Studies on DNA binding behaviour of biologically active transition metal complexes of new tetradentate N2O2 donor Schiff bases: inhibitory activity against bacteria.

    PubMed

    Sobha, S; Mahalakshmi, R; Raman, N

    2012-06-15

    A series of Cu(II), Ni(II) and Zn(II) complexes of the type ML have been synthesized with Schiff bases derived from o-acetoacetotoluidide, 2-hydroxybenzaldehyde and o-phenylenediamine/1,4-diaminobutane. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytic in nature. All the six metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The analytical data helped to elucidate the structure of the metal complexes. The Schiff bases are found to act as tetradentate ligands using N(2)O(2) donor set of atoms leading to a square-planar geometry for the complexes around all the metal ions. The binding properties of metal complexes with DNA were investigated by absorption spectra, viscosity measurements and cyclic voltammetry. Detailed analysis reveals that the metal complexes intercalate into the DNA base stack as intercalators. All the metal complexes cleave the pUC19 DNA in presence of H(2)O(2.) The Schiff bases and their complexes have been screened for their antibacterial activity against five bacterial strains (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus epidermidis, Klebsiella pneumoniae) by disk diffusion method. All the metal complexes have potent biocidal activity than the free ligands.

  3. Semiconductor Gas Sensors Based on Pd/SnO2 Nanomaterials for Methane Detection in Air

    NASA Astrophysics Data System (ADS)

    Fedorenko, George; Oleksenko, Ludmila; Maksymovych, Nelly; Skolyar, Galina; Ripko, Oleksandr

    2017-05-01

    Semiconductor sensors based on nanosized Pd-containing tin dioxide have been obtained by a sol-gel technique. Semiconductor gas-sensitive materials were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) methods. Influence of Pd additives on sensitivity of the sensors to methane has been studied. Temperature dependences of electrical resistance in air and sensor response to methane on palladium content for the sensors based on nanosized materials Pd/SnO2 have been investigated.

  4. Validity of actinometry to monitor oxygen atom concentration in microwave discharges created by surface wave in O2-N2 mixtures

    NASA Astrophysics Data System (ADS)

    Granier, A.; Chéreau, D.; Henda, K.; Safari, R.; Leprince, P.

    1994-01-01

    The validity of actinometry to monitor oxygen atom concentration in O2-N2 microwave discharges created by surface wave is investigated. The plasma is created with a gas flow in a quartz tube of inner diameter 16 mm at pressures in the Torr range. First, it is shown that the reliability of actinometry can be deduced from the longitudinal profile of the actinometry signal. Second, absolute concentrations of oxygen atoms are estimated from the experimental actinometry signal and agree satisfactorily with concentrations simultaneously measured by vacuum ultraviolet (VUV) absorption downstream from the plasma. Moreover, upon varying the nitrogen percentage (0%-100%), it is evidenced that the actinometry signal is proportional to the concentration measured by VUV absorption. Furthermore, it is evidenced that the oxygen dissociation rate is only 2% in pure oxygen plasmas, while it reaches 15% (433 MHz) or 30% (2450 MHz) for mixtures containing more than 20% of nitrogen. This drastic increase in [O] upon the addition of N2 is extensively discussed and, finally, attributed to a decrease in the recombination frequency of oxygen atoms on the quartz wall, in the presence of nitrogen.

  5. Indoor air disinfection using a polyester supported TiO2 photo-reactor.

    PubMed

    Paschoalino, M P; Jardim, W F

    2008-12-01

    Among the decontamination methods applicable to indoor air, heterogeneous photocatalysis has received increasing attention in recent years. This decontamination method is based on the UV irradiation of a solid catalyst, normally TiO2, aiming at the generation of highly reactive hydroxyl radicals. In this work, a novel way to prepare the photocatalyst was used, incorporating pure P-25 TiO2 (Degussa) into polyester orthophthalic polymer. The film was coated onto the walls of a PVC reactor with a concentric 30 W germicidal lamp (254 nm). The efficiency of this prototype was evaluated against fungi and bacteria elimination in a 67 m3 confined room. The system was very efficient for bacteria reduction, decreasing the bacterial count to below the detection limit (1 CFU/plate during 30-min sampling) after 2 h of operation at 195 l/min. For fungi, the gas-phase reactor showed to be less efficient and silver doping of the catalyst showed no increase in biocide activity. The use of a photocatalytic reactor based on TiO2 incorporated onto polyester orthophtalic polymer has been tested at 195 l/min, showing good performance in the air disinfection of a 67 m3 room.

  6. Synergy effect of heat and UV photons on bacterial-spore inactivation in an N2-O2 plasma-afterglow sterilizer

    NASA Astrophysics Data System (ADS)

    Boudam, M. K.; Moisan, M.

    2010-07-01

    As a rule, medical devices (MDs) made entirely from metals and ceramics can withstand, for sterilization purposes, elevated temperatures such as those encountered in autoclaves (moist heat >=120 °C) or Poupinel (Pasteur) ovens (dry heat >=160 °C). This not the case with MDs containing polymers: 70 °C seems to be a limit beyond which their structural and functional integrity will be compromised. Nonetheless, all the so-called low-temperature sterilization techniques, relying essentially on some biocidal chemistry (e.g. ethylene oxide, H2O2, O3), are operated at temperatures close to 65 °C, essentially to enhance the chemical reactivity of the biocidal agent. Based on this fact, we have examined the influence of increasing the temperature of the polystyrene Petri dish containing B. atrophaeus bacterial spores when exposing them to UV radiation coming from an N2-O2 flowing plasma afterglow. We have observed that, for a given UV radiation intensity, the inactivation rate increases with the temperature of the Petri dish, provided heat and UV photons are applied simultaneously, a clear case of synergistic effect. More specifically, it means that (i) simply heating the spores at temperatures below 65 °C without irradiating them with UV photons does not induce mortality; (ii) there is no additional increase in the inactivation rate when the Petri has been pre-heated and then brought back to ambient temperature before the spores are UV irradiated; (iii) no additional inactivation results from post-heating spores previously inactivated with UV radiation. Undoubtedly, the synergistic effect shows up only when the physico-chemical agents (UV photons and temperature) are simultaneously in action.

  7. Treatment of aniline by catalytic wet air oxidation: comparative study over CuO/CeO2 and NiO/Al2O3.

    PubMed

    Ersöz, Gülin; Atalay, Süheyda

    2012-12-30

    The treatment of aniline by catalytic wet air oxidation (CWAO) was studied in a bubble reactor. The experiments were performed to investigate the effects of catalyst loading, temperature, reaction time, air flow rate, and pressure on aniline removal. The catalytic effects of the prepared nanostructured catalysts, CuO/CeO(2) (10% wt) and NiO/Al(2)O(3) (10% wt), on the CWAO treatment efficiency were also examined and compared. The prepared catalysts seem to be active having an aniline removal of 45.7% with CuO/CeO(2) and 41.9% with NiO/Al(2)O(3). The amount of N(2) formed was approximately the same for both of the catalysts.

  8. Two-dimensional fluid simulation on transient behavior and plasma uniformity in pulsed RF CCP sustained in SiH4 /N2/O2

    NASA Astrophysics Data System (ADS)

    Jia, Wen-Zhu; Wang, Xi-Feng; Song, Yuan-Hong; Wang, You-Nian

    2017-04-01

    Improving plasma uniformity during plasma processing in the microelectronics industry is of critical importance to the quality of etching or deposition. Compared to continuous wave (CW) plasmas, pulsed plasmas have drawn much attention with the introduction of additional pulse parameters, which would be helpful to improve the plasma properties. In this paper, a two-dimensional fluid model is developed to investigate a pulsed radio-frequency capacitively coupled plasma (CCP) sustained in SiH4/N2/O2 mixture at fixed operating conditions of 70V rf power, 300 mTorr (40 Pa) gas pressure and an SiH4/N2/O2 gas ratio of 2.5/92.5/5. First, we study the temporal dynamics of densities of the electron, positive ion and negative ion, at different positions in the pulsed CCP. Under the operation conditions, charged particles, instead of neutral particles, may basically respond to the applied modulated power. The electron density in the bulk could approach a quasi-steady value by the end of the activeglow. However, the achievement of a quasi-steady state of plasma like that in the CW condition not only depends on enough activeglow time of the pulse discharge but also relies on the observed position in the discharge. In addition, we investigate the impact of pulse parameters on plasma characteristics, showing that the radial inhomogeneity of plasma caused by the edge effect can be effectively suppressed by controlling the duty cycle (DC) rather than the pulse repetition frequency (PRF). Improvement of the plasma uniformity in pulsed discharge is due to the competition between the edge effects during the activeglow and diffusion of charged species during the afterglow. Moreover, the electron density undergoes a local minimum value in the temporal profile before it rises sharply beyond that of CW discharge, since production of electrons is less than loss by the spatial movement at the very beginning of one pulse. Also, there appears to be a peak value of ion bombardment energy at

  9. Design strategies for P-containing fuels adaptable CeO2-MoO3 catalysts for DeNO(x): significance of phosphorus resistance and N2 selectivity.

    PubMed

    Chang, Huazhen; Jong, Min Tze; Wang, Chizhong; Qu, Ruiyang; Du, Yu; Li, Junhua; Hao, Jiming

    2013-10-15

    Phosphorus compounds from flue gas have a significant deactivation effect on selective catalytic reduction (SCR) DeNOx catalysts. In this work, the effects of phosphorus over three catalysts (CeO2, CeO2-MoO3, and V2O5-MoO3/TiO2) for NH3-SCR were studied, and characterizations were performed aiming at a better understanding of the behavior and poisoning mechanism of phosphorus over SCR catalysts. The CeO2-MoO3 catalyst showed much better catalytic behavior with respect to resistance to phosphorus and N2 selectivity compared with V2O5-MoO3/TiO2 catalyst. With addition of 1.3 wt % P, the SCR activity of V2O5-MoO3/TiO2 decreased dramatically at low temperature due to the impairment of redox property for NO oxidation; meanwhile, the activity over CeO2 and CeO2-MoO3 catalysts was improved. The superior NO oxidation activity contributes to the activity over P-poisoned CeO2 catalyst. The increased surface area and abundant acidity sites contribute to excellent activity over CeO2-MoO3 catalyst. As the content of P increased to 3.9 wt %, the redox cycle over CeO2 catalyst (2CeO2 ↔ Ce2O3 + O*) was destroyed as phosphate accumulated, leading to the decline of SCR activity; whereas, more than 80% NOx conversion and superior N2 selectivity were obtained over CeO2-MoO3 at T > 300 °C. The effect of phosphorus was correlated with the redox properties of SCR catalyst for NH3 and NO oxidation. A spillover effect that phosphate transfers from Ce to Mo in calcination was proposed.

  10. Constraining N2O emissions since 1940 using firn air isotope measurements in both hemispheres

    NASA Astrophysics Data System (ADS)

    Prokopiou, Markella; Martinerie, Patricia; Sapart, Célia J.; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Bernard, Sophie; Kaiser, Jan; Levin, Ingeborg; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik S. W.; Röckmann, Thomas

    2017-04-01

    N2O is currently the third most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes over the past decades, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using new and previously published firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290 ± 1) nmol mol-1 in 1940 to (322 ± 1) nmol mol-1 in 2008, the isotopic composition of atmospheric N2O decreased by (-2.2 ± 0.2) ‰ for δ15Nav, (-1.0 ± 0.3) ‰ for δ18O, (-1.3 ± 0.6) ‰ for δ15Nα, and (-2.8 ± 0.6) ‰ for δ15Nβ over the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric box and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to fix at 123 years. The average isotopic composition over the investigated period is δ15Nav = (-7.6 ± 0.8) ‰ (vs. air-N2), δ18O = (32.2 ± 0.2) ‰ (vs. Vienna Standard Mean Ocean Water - VSMOW) for δ18O, δ15Nα = (-3.0 ± 1.9) ‰ and δ15Nβ = (-11.7 ± 2.3) ‰. δ15Nav, and δ15Nβ show some temporal variability, while for the other signatures the error bars of the reconstruction are too large to retrieve reliable temporal changes. Possible processes that may explain trends in 15N are discussed. The 15N site preference ( = δ15Nα - δ15Nβ) provides evidence of a shift in emissions from denitrification to nitrification, although the uncertainty envelopes are large.

  11. Observation of positronium formation with inner orbital electrons for O2, CO2, C2H2, and N2O using PsARS

    NASA Astrophysics Data System (ADS)

    Edwards, J. J.; Kauppila, W. E.; Miller, E. G.; Stein, T. S.; Surdutovich, E.

    2006-05-01

    We are investigating ortho- and para-positronium (Ps) formation for positrons interacting with simple gas molecules in a gas scattering cell using Ps annihilation ratio spectroscopy (PsARS)[1]. These measurements involve the detection of two gamma rays in coincidence for energy windows (a) centered at 511 keV resulting from the decay of short-lived (0.1 ns) para-Ps and the destruction of longer-lived (0.1 μs) ortho-Ps at the scattering cell walls, and (b) from 300 to 460 keV resulting from the three gamma decay of ortho-Ps. By taking the ratios of these signals versus positron impact energy we find we are able to compare the resulting curves with that obtained for argon as a reference. These comparisons reveal departures from the argon curve at well defined energies and are interpreted as Ps formation with inner orbital electrons. The fractions of the overall Ps formation cross-section due to inner orbital electrons are estimated to be as high as 30% for O2, 25% for CO2, 15% for N2O and 5% for C2H2 near their respective threshold energies. [1] W.E. Kauppila, E.G. Miller, H.F.M. Mohamed, K. Pipinos, T.S. Stein, E. Surdutovich, Phys. Rev. Lett. 93, 113401 (2004).

  12. Saturated fluorescence measurements of the hydroxyl radical in laminar high-pressure C2H6/O2/N2 flames

    NASA Technical Reports Server (NTRS)

    Carter, Campbell D.; King, Galen B.; Laurendeau, Normand M.

    1992-01-01

    Saturation of a transition of the OH molecule in high-pressure flames is demonstrated by obtaining saturation curves in C2H6/O2/N2 laminar flames at 1, 6.1, 9.2, and 12.3 atm. Quantitative fluorescence measurements of OH number density at pressures to 12.3 atm are presented. To assess the efficacy of the balanced cross-rate model for high-pressure flames, laser-saturated fluorescence measurements, which were calibrated in an atmospheric-pressure flame, are compared with absorption measurements at 3.1 and 6.1 atm. At 3.1 atm the absorption and fluorescence measurements compare well. At 6.1 atm, however, the concentrations given by lasre-saturated fluorescence are about 25 percent lower than the absorption values, indicating some depletion of the laser-coupled levels beyond that at atmospheric pressure. By using a reasonable estimate for the finite sensitivity to quenching, it is anticipated that fluorescence measurements that are calibrated at 1 atm can be applied to flames at about 10 atm with absolute errors within +/- 50 percent.

  13. Dissociation cross sections for N2 + N → 3N and O2 + O → 3O using the QCT method

    NASA Astrophysics Data System (ADS)

    Mankodi, Tapan K.; Bhandarkar, Upendra V.; Puranik, Bhalchandra P.

    2017-05-01

    Cross sections for the homo-nuclear atom-diatom collision induced dissociations (CIDs): N2 + N and O2 + O are calculated using Quasi-Classical Trajectory (QCT) method on ab initio Potential Energy Surfaces (PESs). A number of studies for these reactions carried out in the past focused on the CID cross section values generated using London-Eyring-Polanyi-Sato PES and seldom listed the CID cross section data. A highly accurate CASSCF-CASPT2 N3 and a new O3 global PES are used for the present QCT analysis and the CID cross section data up to 30 eV relative energy are also published. In addition, an interpolating scheme based on spectroscopic data is introduced that fits the CID cross section for the entire ro-vibrational spectrum using QCT data generated at chosen ro-vibrational levels. The rate coefficients calculated using the generated CID cross section compare satisfactorily with the existing experimental and theoretical results. The CID cross section data generated will find an application in the development of a more precise chemical reaction model for Direct Simulation Monte Carlo code simulating hypersonic re-entry flows.

  14. Dissociation cross sections for N2 + N → 3N and O2 + O → 3O using the QCT method.

    PubMed

    Mankodi, Tapan K; Bhandarkar, Upendra V; Puranik, Bhalchandra P

    2017-05-28

    Cross sections for the homo-nuclear atom-diatom collision induced dissociations (CIDs): N2 + N and O2 + O are calculated using Quasi-Classical Trajectory (QCT) method on ab initio Potential Energy Surfaces (PESs). A number of studies for these reactions carried out in the past focused on the CID cross section values generated using London-Eyring-Polanyi-Sato PES and seldom listed the CID cross section data. A highly accurate CASSCF-CASPT2 N3 and a new O3 global PES are used for the present QCT analysis and the CID cross section data up to 30 eV relative energy are also published. In addition, an interpolating scheme based on spectroscopic data is introduced that fits the CID cross section for the entire ro-vibrational spectrum using QCT data generated at chosen ro-vibrational levels. The rate coefficients calculated using the generated CID cross section compare satisfactorily with the existing experimental and theoretical results. The CID cross section data generated will find an application in the development of a more precise chemical reaction model for Direct Simulation Monte Carlo code simulating hypersonic re-entry flows.

  15. Effects of O 2 and N 2/H 2 plasma treatments on the neuronal cell growth on single-walled carbon nanotube paper scaffolds

    NASA Astrophysics Data System (ADS)

    Yoon, Ok Ja; Lee, Hyun Jung; Jang, Yeong Mi; Kim, Hyun Woo; Lee, Won Bok; Kim, Sung Su; Lee, Nae-Eung

    2011-08-01

    The O 2 and N 2/H 2 plasma treatments of single-walled carbon nanotube (SWCNT) papers as scaffolds for enhanced neuronal cell growth were conducted to functionalize their surfaces with different functional groups and to roughen their surfaces. To evaluate the effects of the surface roughness and functionalization modifications of the SWCNT papers, we investigated the neuronal morphology, mitochondrial membrane potential, and acetylcholine/acetylcholinesterase levels of human neuroblastoma during SH-SY5Y cell growth on the treated SWCNT papers. Our results demonstrated that the plasma-chemical functionalization caused changes in the surface charge states with functional groups with negative and positive charges and then the increased surface roughness enhanced neuronal cell adhesion, mitochondrial membrane potential, and the level of neurotransmitter in vitro. The cell adhesion and mitochondrial membrane potential on the negatively charged SWCNT papers were improved more than on the positively charged SWCNT papers. Also, measurements of the neurotransmitter level showed an enhanced acetylcholine level on the negatively charged SWCNT papers compared to the positively charged SWCNT papers.

  16. Low Temperature Heat Capacities and Standard Molar Enthalpy of Formation of 2-Pyrazinecarboxylic Acid (C5H4N2O2)(s).

    PubMed

    Kong, Yu-Xia; Di, You-Ying; Yang, Wei-Wei; Gao, Sheng-Li; Tan, Zhi-Cheng

    2010-06-01

    Low-temperature heat capacities of 2-pyrazinecarboxylic acid (C5H4N2O2)(s) were measured by a precision automated adiabatic calorimeter over the temperature range from 78 to 400 K. A polynomial equation of heat capacities as a function of temperature was fitted by least squares method. Based on the fitted polynomial, the smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15 K were calculated and tabulated at 10 K intervals. The constant-volume energy of combustion of the compound at T = 298.15 K was measured by a precision rotating-bomb combustion calorimeter to be ΔcU = -(17839.40 ± 7.40) J g-1. The standard molar enthalpy of combustion of the compound was determined to be ΔcH0m = -(2211.39 ± 0.92) KJ mol-1, according to the definition of combustion enthalpy. Finally, the standard molar enthalpy of formation of the compound was calculated to be ΔfH0m = -(327.82 ± 1.13) kJ mol-1 in accordance with Hess law.

  17. Computer program of data reduction procedures for facilities using CO2-N2-O2-Ar equilibrium real-gas mixtures

    NASA Technical Reports Server (NTRS)

    Miller, C. G., III

    1972-01-01

    Data reduction procedures for determining free-stream and post-normal-shock flow conditions are presented. These procedures are applicable to flows of CO2, N2, O2, Ar, or mixtures of these gases and include the effects of dissociation and ionization. The assumption of thermochemical equilibrium free-stream and post-normal-shock flow is made. Although derived primarily to meet the immediate needs of an expansion tube of a hot gas radiation research facility, these procedures are applicable to any supersonic or hypersonic test facility using these gases or mixtures thereof. The data reduction procedures are based on combinations of three of the following flow parameters measured in the immediate vicinity of the test section: (1) stagnation pressure behind normal shock, (2) free-stream static pressure, (3) stagnation-point heat-transfer rate, (4) free-stream velocity, and (5) free-stream density. Thus, these procedures do not depend explicitly upon measured or calculated upstream flow parameters. The procedures are incorporated into a single computer program written in FORTRAN IV language. A listing of this computer program is presented, along with a description of the inputs required and a sample of the data printout.

  18. Ru(II) complexes of N 4 and N 2O 2 macrocyclic Schiff base ligands: Their antibacterial and antifungal studies

    NASA Astrophysics Data System (ADS)

    Shanker, Kanne; Rohini, Rondla; Ravinder, Vadde; Reddy, P. Muralidhar; Ho, Yen-Peng

    2009-07-01

    Reactions of [RuCl 2(DMSO) 4] with some of the biologically active macrocyclic Schiff base ligands containing N 4 and N 2O 2 donor group yielded a number of stable complexes, effecting complete displacement of DMSO groups from the complex. The interaction of tetradentate ligand with [RuCl 2(DMSO) 4] gave neutral complexes of the type [RuCl 2(L)] [where L = tetradentate macrocyclic ligand]. These complexes were characterized by elemental, IR, 1H, 13C NMR, mass, electronic, thermal, molar conductance and magnetic susceptibility measurements. An octahedral geometry has been proposed for all complexes. All the macrocycles and macrocyclic Ru(II) complexes along with existing antibacterial drugs were screened for antibacterial activity against Gram +ve ( Bacillus subtilis, Staphylococcus aureus) and Gram -ve ( Escherichia coli, Klebsiella pneumonia) bacteria. All these compounds were found to be more active when compared to streptomycin and ampicillin. The representative macrocyclic Schiff bases and their complexes were also tested in vitro to evaluate their activity against fungi, namely, Aspergillus flavus and Fusarium species.

  19. Feasibility of measuring temperature and density fluctuations in air using laser-induced O2 fluorescence

    NASA Technical Reports Server (NTRS)

    Massey, G. A.; Lemon, C. J.

    1984-01-01

    A tunable line-narrowed ArF laser can selectively excite several rotation al lines of the Schumann-Runge band system of O2 in air. The resulting ultraviolet fluorescence can be monitored at 90 deg to the laser beam axis, permitting space and time resolved observation of density and temperature fluctuations in turbulence. Experiments and calculations show that + or - 1 K, + or - 1 percent density, 1 cu mm spatial, and 1 microsecond temporal resolution can be achieved simultaneously under some conditions.

  20. Can TiO2-based photocatalytic textiles be used to improve the urban air quality?

    NASA Astrophysics Data System (ADS)

    Ródenas, Mila; Fages, Eduardo; Fatarella, Enrico; Herrero, David; Castagnoli, Lidia; Borràs, Esther; Vera, Teresa; Gómez, Tatiana; Catota, Marlon; Carreño, Javier; Hernández, Daniel; Gimeno, Cristina; López, Ramón; Muñoz, Amalia

    2017-04-01

    Despite current legislation and efforts made to improve urban air quality, significant negative effects still persist. That is the case of traffic, which impact on air pollution is a growing problem. For this reason, depollution measures are necessary to reach safer air quality levels. Recently, the use of titanium dioxide (TiO2) based photocatalytic self-cleaning and de-polluting materials has been considered to remove air pollutants, especially NOx. TiO2 can be found in the market under different formats for environmental purposes, and its effectiveness depends not only on the support (concrete, paints, etc) but also on the impregnation method (layer, embedded, etc). By combining laboratory and field campaigns, the LIFE PHOTOCITYTEX project was conceived to demonstrate the effectiveness of using TiO2-based photocatalytic nanomaterials in textiles as a way of alleviating the air pollution in urban areas. Within the project, which is already within its last year, two one-year extensive passive dosimetric campaigns have already been completed to assess their impact on the selected urban sites, measuring before and after the installation of the photocatalytic textile prototypes, respectively. Also, intensive active measurement campaigns (using active dosimetry, monitors and instrumentation for physical parameters) have been conducted to account for winter and summer conditions. Besides, lab-tests have been concluded to determine optimal photocatalytic formulations on textiles, and these have been tested at the EUPHORE simulation chambers under typical environmental conditions of various European cities. Besides the effect on NOx, which has been the main focus of the study, VOCs formation and abatement has been assessed, yielding in a better overall understanding of the whole process and its implications. Very promising results on the deep reduction of NOx have been observed at EUPHORE. From the calculation of the uptake coefficient, a mathematical model tool foresees

  1. Model of Odd N in the Terrestrial Thermosphere: 1. A First Principles Calculation of the NO2 Potential Energy Surfaces Relevant to the Production of NO via the N(2D)+O2 Reaction.

    NASA Astrophysics Data System (ADS)

    Dothe, H.; Braunstein, M.; Duff, J. W.; Sharma, R. D.

    2001-12-01

    The daytime observation of 5.3 μ m thermospheric emission from the NO fundamental vibration-rotation band by the interferometer aboard the cryogenic infrared radiance instrumentation for shuttle (CIRRIS 1A) has provided important insight into the phenomenology of NO formation. The four major mechanisms to the 5.3 μ m emission considered by previous modeling are solar pumping, inelastic collisions of O with NO(v=0), the reactions of N(2D) with O2, and the reactions of N(4S) with O2. It has previously been shown that the reaction of N(4S) with O2 is consistent with rotationally nonthermal 5.3 μ m emission, while the N(2D)+O2 reaction has been assumed to contribute to rotationally thermal emission. The assumption of a thermal rotational distribution from the N(2D)+O2 reaction cannot be confirmed by the CIRRIS 1A data. The existence of a significant fraction of nonthermal atoms in the tail of the N(2D) energy distribution function (EDF) in the daylit thermosphere was demonstrated earlier (AGU Spring 2001). Therefore the investigation of possible nonthermal behavior in NO formation via the N(2D)+O2 reaction in the daylit and aurorally dosed thermosphere requires energy dependent cross sections for the reaction between N(2D) and O2. To calculate the N(2D)+O2 cross sections, potential energy surfaces (PES) of the NO2 system are required. The output of these calculations include the energy dependent cross sections and the vibrational and rotational distribution of the nascent NO needed for accurate calculation of the cooling rates due to 5.3 μ m emission. This work concentrates on the first step towards the calculation of such cross sections, the ab initio calculations of the NO2 PES. Previous existing PES, using different basis sets and electron correlation levels, have shown disagreements in the magnitude of the barriers for the lowest lying doublet surfaces in the reaction entrance channel. Comparative results from our calculations are presented here, showing PES

  2. Photocatalytic performance of electrospun CNT/TiO2 nanofibers in a simulated air purifier under visible light irradiation.

    PubMed

    Wongaree, Mathana; Chiarakorn, Siriluk; Chuangchote, Surawut; Sagawa, Takashi

    2016-11-01

    The photocatalytic treatment of gaseous benzene under visible light irradiation was developed using electrospun carbon nanotube/titanium dioxide (CNT/TiO2) nanofibers as visible light active photocatalysts. The CNT/TiO2 nanofibers were fabricated by electrospinning CNT/poly(vinyl pyrrolidone) (PVP) solution followed by the removal of PVP by calcination at 450 °C. The molar ratio of CNT/TiO2 was fixed at 0.05:1 by weight, and the quantity of CNT/TiO2 loaded in PVP solution varied between 30 and 60 % wt. CNT/TiO2 nanofibers have high specific surface area (116 m(2)/g), significantly higher than that of TiO2 nanofibers (44 m(2)/g). The photocatalytic performance of the CNT/TiO2 nanofibers was investigated by decolorization of 1 × 10(-5) M methylene blue (MB) dye (in water solution) and degradation of 100 ppm gaseous benzene under visible light irradiation. The 50-CNT/TiO2 nanofibers (calcined CNT/TiO2 nanofibers fabricated from a spinning solution of 50 % wt CNT/TiO2 based on PVP) had higher MB degradation efficiency (58 %) than did other CNT/TiO2 nanofibers and pristine TiO2 nanofibers (15 %) under visible light irradiation. The photocatalytic degradation of gaseous benzene under visible light irradiation on filters made of 50-CNT/TiO2 nanofibers was carried out in a simulated air purifier system. Similar to MB results, the degradation efficiency of gaseous benzene by 50-CNT/TiO2 nanofibers (52 %) was higher than by other CNT/TiO2 nanofibers and pristine TiO2 nanofibers (18 %). The synergistic effects of the larger surface area and lower band gap energy of CNT/TiO2 nanofibers were presented as strong adsorption ability and greater visible light adsorption. The CNT/TiO2 nanofiber prepared in this study has potential for use in air purifiers to improve air treatment efficiency with less energy.

  3. The 2140 cm(exp -1) (4.673 Microns) Solid CO Band: The Case for Interstellar O2 and N2 and the Photochemistry of Non-Polar Interstellar Ice Analogs

    NASA Technical Reports Server (NTRS)

    Elsila, Jamie; Allamandola, Louis J.; Sandford, Scott A.; Witteborn, Fred C. (Technical Monitor)

    1996-01-01

    The infrared spectra of CO frozen in non-polar ices containing N2, CO2, O2, and H2O, and the ultraviolet photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140/cm (4.673 micrometer) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing non-polar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a very good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices.

  4. Air blood barrier phenotype correlates with alveolo-capillary O2 equilibration in hypobaric hypoxia.

    PubMed

    Beretta, Egidio; Lanfranconi, Francesca; Grasso, Gabriele Simone; Bartesaghi, Manuela; Alemayehu, Hailu Kinfu; Pratali, Lorenza; Catuzzo, Bruna; Giardini, Guido; Miserocchi, Giuseppe

    2017-12-01

    The O2 diffusion limitation across the air blood barrier (DO2 and subcomponents Dm and Vc) was evaluated in 17 healthy participants exposed to hypobaric hypoxia (HA, 3840m, PIO2 ∼90mmHg). A 10% decrease in alveolar volume (VA) in all participants suggested the development of sub-clinical interstitial lung edema. In >80% of participants DO2/VA increased, reflecting an individual strategy to cope with the hypoxia stimulus by remodulating Vc or Dm. Opposite changes in Dm/Vc ratio were observed and participants decreasing Vc showed reduced alveolar blood capillary transit time. The interplay between diffusion and perfusion (cardiac output) was estimated in order to investigate the individual adaptive response to hypoxia. It appears remarkable that despite individual differences in the adaptive response to HA, diffusion limitation did not exceed ∼11% of the alveolar-venous PO2 gradient, revealing an admirable functional design of the air-blood barrier to defend the O2 diffusion/perfusion function when facing hypobaric hypoxia corresponding to 50mmHg decreased PAO2. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Air-suspended TiO2-based HCG reflectors for visible spectral range

    NASA Astrophysics Data System (ADS)

    Hashemi, Ehsan; Bengtsson, Jörgen; Gustavsson, Johan; Carlsson, Stefan; Rossbach, Georg; Haglund, Åsa

    2015-02-01

    For GaN-based microcavity light emitters, such as vertical-cavity surface-emitting lasers (VCSELs) and resonant cavity light emitting diodes (RCLEDs) in the blue-green wavelength regime, achieving a high reflectivity wide bandwidth feedback mirror is truly challenging. The material properties of the III-nitride alloys are hardly compatible with the conventional distributed Bragg reflectors (DBRs) and the newly proposed high-contrast gratings (HCGs). Alternatively, at least for the top outcoupling mirror, dielectric materials offer more suitable material combinations not only for the DBRs but also for the HCGs. HCGs may offer advantages such as transverse mode and polarization control, a broader reflectivity spectrum than epitaxially grown DBRs, and the possibility to set the resonance wavelength after epitaxial growth by the grating parameters. In this work we have realized an air-suspended TiO2 grating with the help of a SiO2 sacrificial layer. The deposition processes for the dielectric layers were fine-tuned to minimize the residual stress. To achieve an accurate control of the grating duty cycle, a newly developed lift-off process, using hydrogen silesquioxan (HSQ) and sacrificial polymethyl-methacrylate (PMMA) resists, was applied to deposit the hard mask, providing sub-10 nm resolution. The finally obtained TiO2/air HCGs were characterized in a micro-reflectance measurement setup. A peak power reflectivity in excess of 95% was achieved for TM polarization at the center wavelength of 435 nm, with a reflectivity stopband width of about 80 nm (FWHM). The measured HCG reflectance spectra were compared to corresponding simulations obtained from rigorous coupled-wave analysis and very good agreement was found.

  6. Are TiO2 nanotubes worth using in photocatalytic purification of air and water?

    PubMed

    Pichat, Pierre

    2014-09-19

    Titanium dioxide nanotubes (TNT) have mainly been used in dye sensitized solar cells, essentially because of a higher transport rate of electrons from the adsorbed photo-excited dye to the Ti electrode onto which TNT instead of TiO2 nanoparticles (TNP) are attached. The dimension ranges and the two main synthesis methods of TNT are briefly indicated here. Not surprisingly, the particular and regular texture of TNT was also expected to improve the photocatalytic efficacy for pollutant removal in air and water with respect to TNP. In this short review, the validity of this expectation is checked using the regrettably small number of literature comparisons between TNT and commercialized TNP referring to films of similar thickness and layers or slurries containing an equal TiO2 mass. Although the irradiated geometrical area differed for each study, it was identical for each comparison considered here. For the removal of toluene (methylbenzene) or acetaldehyde (ethanal) in air, the average ratio of the efficacy of TNT over that of TiO2 P25 was about 1.5, and for the removal of dyes in water, it was around 1. This lack of major improvement with TNT compared to TNP could partially be due to TNT texture disorders as seems to be suggested by the better average performance of anodic oxidation-prepared TNT. It could also come from the fact that the properties influencing the efficacy are more numerous, their interrelations more complex and their effects more important for pollutant removal than for dye sensitized solar cells and photoelectrocatalysis where the electron transport rate is the crucial parameter.

  7. Synthesis and spectroscopic characterization of some transition metal complexes of a new hexadentate N(2)S(2)O(2) Schiff base ligand.

    PubMed

    Sarkar, Saikat; Dey, Kamalendu

    2005-11-01

    A novel interesting hexadentate dibasic N(2)S(2)O(2) donor Schiff base ligand, H(4)dcsalpte, was synthesized by the condensation of 3-formylsalicylic acid and 1,2-di(o-aminophenylthio)ethane and characterized. The reactions of the ligand with different metal(II/III)salts under varied reaction conditions afforded a series of metal complexes. The ligand, H(4)dcsalpte, behaves either as a dibasic or neutral hexadentate one, depending on the reaction conditions. Structural investigations on the ligand and their complexes have been made based on elemental analyses, molar conductance values, magnetic moment values, cryomagnetic and spectral (UV-vis, IR, (1)H NMR, and Mössbauer) data. Based on magnetic susceptibility, Mössbauer and electronic spectral data the iron(III) complex [Fe(III)(H(2)dcsalpte)]ClO(4) (8), isolated in the present investigation, it is inferred that the spin states 5/2 and 1/2 are in equilibrium. Similarly a tri-iron(III) complex [Fe(III)(3)(H(2)dcsalpte)(H(3)dcsalpte)Cl(3)]Cl(3) (7), isolated in this study, has been inferred to contain two iron(III) sites in tetrahedral environment and one in the octahedral environment. The aerial oxidation of an equimolar mixture of H(4)dcsalpte and Co(CH(3)COO)(2).4H(2)O in ethanol under reflux gave two products, [Co(H(2)dcsalpte)]CH(3)COO (10) and [(Hbtcsaldm)Co(Hbvcsaldm)] (11), a cobalt(III) complex bound to two dissimilar tridentate NSO donor ligands formed as a result of the oxidative cleavage of the CS bond. In the complex 11, Hbtcsaldm stands for the dianion of the tridentate Schiff base ligand N-(2'-benzenethiol)-3-carboxysalicylaldimine and Hbvcsaldm stands for the mono anion of the tridentate Schiff base ligand N-(benzene-2'-S-vinyl)-3-carboxysalicylaldimine, both being formed as a result of the oxidative cleavage of H(4)dcsalpte.

  8. Synthesis, spectroscopic characterization, thermal studies, catalytic epoxidation and biological activity of chromium and molybdenum hexacarbonyl bound to a novel N 2O 2 Schiff base

    NASA Astrophysics Data System (ADS)

    Abdel Aziz, Ayman A.

    2010-08-01

    Complexes of M(CO) 6 (M = Cr and Mo) with novel Schiff base N,N'-bis(salicylidene)4,5-dichloro-1,2-phenylenediamine (H 2L) were prepared in benzene in two different conditions: (i) under reduced pressure resulting the dicarbonyl precursors [Cr(CO) 2(H 2L)] and [Mo(CO) 2(L)] and (ii) in air resulting the oxo complex [Cr(O)(L)] and the dioxo complex [Mo(O) 2(L)]. The complexes were characterized by elemental analysis, IR, 1H NMR, mass spectrometry, and magnetic measurement. Thermal behaviors of the complexes were also studied by using thermogravimetric analysis (TGA). The catalytic activity of the novel complexes in the epoxidation of cyclooctene, cyclohexene, 1-octene and 1-hexene with tert-butyl-hydroperoxide (TBHP) in methylene chloride was investigated. The antimicrobial activities of the ligand and their complexes have been screened against various strains of bacteria and fungi and the results have been compared with some known antibiotics.

  9. Evaluation of clay-TiO2 nanocomposite efficiency on the photocatalytic elimination of a model hydrophobic air pollutant.

    NASA Astrophysics Data System (ADS)

    Cervini-Silva, J.; Kibanova, D.; Destaillats, H.

    2008-12-01

    Clay-supported TiO2 photocatalysts can potentially improve the performance of air treatment technologies due to enhanced adsorption and reactivity of volatile organic compounds (VOCs). In this study, a bench-top photocatalytic flow reactor was used to evaluate hectorite-TiO2 and kaolinite-TiO2, two novel composite materials synthesized in our laboratory. Toluene, a model hydrophobic VOC and a common indoor air pollutant, was introduced in the air stream at realistic concentrations and reacted under UVA (?max = 365 nm) or UVC (?max = 254 nm) irradiation. The UVC lamp presented secondary emission at 185 nm, leading to the formation of ozone and other short-lived reactive species. Performance of clay-TiO2 composites was compared with that of pure TiO2 (Degussa P25) and with UV irradiation in the absence of photocatalyst under identical conditions. Films of clay-TiO2 composites and of P25 were prepared by a dip- coating method on the surface of Raschig rings placed inside the flow reactor. An upstream toluene concentration of 150 ppbv was generated by diluting a constant vapor flow with dry air, or with humid air at 10, 33, and 66 % relative humidity (RH). Toluene concentrations downstream were determined by collecting Tenax-TA ® sorbent tubes and subsequent thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS) analysis. The fraction of toluene removed, %R, and the reaction rate, Tr, were calculated for each experimental condition from the concentration changes registered with and without UV irradiation. Use of UVC light (UV/TiO2/O3) led to overall higher reactivity, which can be partially attributed to contribution of gas phase reactions by O3 and other short-lived species. When the reaction rate was normalized by the light irradiance, Tr/Iλ, the UV/TiO2 reaction under UVA irradiation was more efficient for samples with a higher content of TiO2 (P25 and Hecto-TiO2), but not for Kao-TiO2. Considering the effect of relative humidity, in all cases reaction

  10. Seasonal cycle of N2O vertical distribution and air sea fluxes over the continental shelf waters off central Chile (˜36°S)

    NASA Astrophysics Data System (ADS)

    Cornejo, Marcela; Farías, Laura; Gallegos, Mauricio

    2007-11-01

    denitrification. Consistent with the evolution of N 2O in the water column over time, the estimated air-sea N 2O fluxes were low or negative in winter (-9.8 to 20 μmol m -2 d -1, Stage I) and higher in spring and summer (up to 195 μmol m -2 d -1, Stage II), after which they declined (Stage III). In spite of the occurrence of ESSW and upwelling events throughout stages II and III, N 2O behaviour should be a response of the biogeochemical evolution associated with biological productivity and concomitant O 2 levels in the water and even in the sediments. The results presented herein confirm that the study area is an important source of N 2O to the atmosphere, with a mean annual N 2O flux of 30.2 μmol m -2 d -1; however, interannual variability could not yet be properly characterized.

  11. Passivation of uranium towards air corrosion by N 2+ and C + ion implantation

    NASA Astrophysics Data System (ADS)

    Arkush, R.; Mintz, M. H.; Shamir, N.

    2000-10-01

    The passivation of uranium surfaces against air corrosion, by ion implantation processes was studied, using surface analysis methods. Implanting 45 keV N +2 and C + ions produces thin modified surface layers with gradual gradients of the corresponding compounds (i.e., nitrides and carbides, respectively), which avoid the formation of discontinuous interfaces typical to coatings. Such gradual interfaces impart excellent mechanical stability and adhesion to the modified layers, in spite of the large misfit between the metal substrate and the implantation on induced compounds. It turns out that these layers provide an almost absolute protection against air corrosion. A rapid initial stage of oxidation of the modified surface layers takes place, forming very thin protective oxidation zones (1-4 nm thick), which practically stop further air oxidation for years. The mechanism of the initial oxidation stage of the modified layers seems to vary with the type of surface (i.e., either nitrides or carbides). However, in any case the protection ability of the formed oxidation products is excellent, probably due to the close match between these compounds and the underlying nitrides or carbides.

  12. Functionalization of graphene by atmospheric pressure plasma jet in air or H2O2 environments

    NASA Astrophysics Data System (ADS)

    Huang, Weixin; Ptasinska, Sylwia

    2016-03-01

    The functionalization of graphene, which deforms its band structure, can result in a metal-semiconductor transition. In this work, we report a facile strategy to oxidize single-layer graphene using an atmospheric pressure plasma jet (APPJ) that generates a variety of reactive plasma species at close to ambient temperature. We systematically characterized the oxygen content and chemical structure of the graphene films after plasma treatment under different oxidative conditions (ambient air atmosphere or hydrogen peroxide solution) by X-ray Photoelectron Spectroscopy (XPS). Plasma-treated graphene films containing more than 40% oxygen were obtained in both oxidative environments. Interestingly, prolonged irradiation led to the reduction of graphene oxides. N-doping of graphene also occurred during the APPJ treatment in H2O2 solution; the nitrogen content of the doped graphene was dependent on the duration of irradiation and reached up to 8.1% within 40 min. Moreover, the H2O2 solution served as a buffer layer that prevented damage to the graphene during plasma irradiation. Four-point probe measurement revealed an increase in sheet resistance of the plasma-treated graphene, indicating the transition of the material property from semi-metallic to semiconducting.

  13. A single-composition CaSi2O2N2:RE (RE=Ce3+/Tb3+, Eu2+, Mn2+) phosphor nanofiber mat: Energy transfer, luminescence and tunable color properties

    NASA Astrophysics Data System (ADS)

    Cui, Bo; Chen, Zhenhua; Zhang, Qinghong; Wang, Hongzhi; Li, Yaogang

    2017-09-01

    CaSi2O2N2:RE (RE = Ce3+/Tb3+, Eu2+, Mn2+) phosphor nanofiber mat has been prepared via the electrospinning process and further annealing treatment. The diameter of nanofiber precursors are generally in a range of 400-600 nm, which exhibits smooth and uniform surface morphology. After removing the polymer template by high temperature treatment, the fabricated mats have been transformed into a phosphor film and maintain uniform nanofiber network microstructures. Photoluminescence (PL) properties of CaSi2O2N2 phosphor nanofiber mat have been activated by Ce3+/Tb3+, Eu2+ and Mn2+. The emission color of CaSi2O2N2:Ce3+/Tb3+, Eu2+, Mn2+ phosphor mats can be adjusted by modifying the concentration of doped Tb3+/Mn2+/Eu2+ and the resultant energy transfer process. Owing to the energy transfer of Ce3+-Tb3+, the emitting color of the phosphor mat can be changed from blue to green. Meanwhile, we still found that the switching of emitting colors from blue to red and blue to yellow can be achieved via the energy transfer of Ce3+-Mn2+ and Ce3+-Eu2+, respectively. We demonstrated a white light emission phosphor nanofiber mat by using CaSi2O2N2 system, which exhibited promising applications for near-UV WLEDs.

  14. Comparative Study of Al2O3 Optical Crystalline Thin Films Grown by Vapor Combinations of Al(CH3)3/N2O and Al(CH3)3/H2O2

    NASA Astrophysics Data System (ADS)

    Kumagai, Hiroshi; Toyoda, Koichi; Matsumoto, Masahiko; Obara, Minoru

    1993-12-01

    We compared the use of nitrous oxide (N2O) and hydrogen peroxide (H2O2) as the oxidant in digital chemical vapor deposition to obtain high-quality optical crystalline thin films of Al2O3. Optical constants and thicknesses of these films were investigated in terms of growth temperature, by using variable-angle spectroscopic ellipsometry.

  15. HITRAN2016: Part I. Line lists for H_2O, CO_2, O_3, N_2O, CO, CH_4, and O_2

    NASA Astrophysics Data System (ADS)

    Gordon, Iouli E.; Rothman, Laurence S.; Tan, Yan; Kochanov, Roman V.; Hill, Christian

    2017-06-01

    The HITRAN2016 database is now officially released. Plethora of experimental and theoretical molecular spectroscopic data were collected, evaluated and vetted before compiling the new edition of the database. The database is now distributed through the dynamic user interface HITRANonline (available at www.hitran.org) which offers many flexible options for browsing and downloading the data. In addition HITRAN Application Programming Interface (HAPI) offers modern ways to download the HITRAN data and use it to carry out sophisticated calculations. The line-by-line lists for almost all of the 47 HITRAN molecules were updated in comparison with the previous compilation (HITRAN2012. Some of the most important updates for major atmospheric absorbers, such as H_2O, CO_2, O_3, N_2O, CO, CH_4, and O_2, will be presented in this talk, while the trace gases will be presented in the next talk by Y. Tan. The HITRAN2016 database now provides alternative line-shape representations for a number of molecules, as well as broadening by gases dominant in planetary atmospheres. In addition, substantial extension and improvement of cross-section data is featured, which will be described in a dedicated talk by R. V. Kochanov. The new edition of the database is a substantial step forward to improve retrievals of the planetary atmospheric constituents in comparison with previous editions, while offering new ways of working with the data. The HITRAN database is supported by the NASA AURA and PDART program grants NNX14AI55G and NNX16AG51G. I. E. Gordon, L. S. Rothman, C. Hill, R. V. Kochanov, Y. Tan, et al. The HITRAN2016 Molecular Spectroscopic Database. JQSRT 2017;submitted. Many spectroscopists and atmospheric scientists worldwide have contributed data to the database or provided invaluable validations. C. Hill, I. E. Gordon, R. V. Kochanov, L. Barrett, J.S. Wilzewski, L.S. Rothman, JQSRT. 177 (2016) 4-14 R.V. Kochanov, I. E. Gordon, L. S. Rothman, P. Wcislo, C. Hill, J. S. Wilzewski

  16. A new Raman-N2 lidar dedicated to air quality survey

    NASA Astrophysics Data System (ADS)

    Royer, P.; Chazette, P.; Lardier, M.; Raut, J.-C.; Sauvage, L.

    2010-05-01

    The Commissariat à l'Energie Atomique (CEA) and the Centre National de la Recherche Scientifique (CNRS) have developed the Lidar Aérosols UltraViolet Aéroporté (LAUVA). The new version of this prototype is now commercialized with success under license by the LEOSPHERE Company with the name EZ LIDAR®. This eye-safe lidar is based on a Nd:YAG laser giving pulses of 16 mJ at 355 nm with a frequency of 20 Hz. The CEA and LEOSPHERE have recently upgraded this instrument into a three detection channels lidar measuring the two elastic cross-polarizations and the Raman-N2 backscatter signal at 387 nm. It is able to retrieve aerosol optical properties (extinction, backscatter coefficients and depolarization ratio) and atmospheric structures (boundary layer height and clouds) with a resolution of 1.5 m along the line-of-sight in analog mode and 15 m in photon-counting mode. This new lidar is particularly well-adapted to air quality survey thanks to a full overlap reached at ~150 m. This compact (90x50x20 cm) and light (less than50 kg) instrument has been integrated into the Mobile Aerosol Station (MAS) onboard a small truck and enables mobile measurements. We will here present and analyze some results obtained around Paris area with this Raman-N2 lidar.

  17. Feasibility of Silver Doped TiO2/Glass Fiber Photocatalyst under Visible Irradiation as an Indoor Air Germicide

    PubMed Central

    Pham, Thanh-Dong; Lee, Byeong-Kyu

    2014-01-01

    This study investigated the feasibility of using Ag-TiO2 photocatalyst supported on glass fiber (Ag-TiO2/GF) prepared by a sol-gel method as an indoor air germicide. An experimental model was designed to investigate the bacterial disinfection efficiency of Staphylococcus (Staph), the most popular bacterium in hospitals in Korea, by the Ag-TiO2/GF photocatalyst. The silver content in Ag/TiO2 was altered from 1 to 10% to investigate the optimal ratio of Ag doped on TiO2/glass fiber (TiO2/GF) for photocatalytic disinfection of Staph. This study confirmed that Ag in Ag-TiO2/GF could work as an electron sink or donor to increase photocatalytic activity and promote the charge separation of electron-hole pairs generated from TiO2 after photon absorption. Ag also acts as an intermediate agent for the transfer of photo-generated electrons from the valence band of TiO2 to an acceptor (O2 gas) to promote photo-oxidation processes. The photocatalytic disinfection activity of Ag-TiO2/GF under visible light increased with the increase in silver content up to 7.5% and then slightly decreased with further increasing silver content. The highest disinfection efficiency and disinfection capacity of Staph using 7.5% Ag-TiO2/GF were 75.23% and 20 (CFU∙s−1∙cm−2) respectively. The medium level of humidity of 60% ± 5% showed better photocatalytic disinfection than the lower (40% ± 5%) or higher (80% ± 5%) levels. PMID:24658408

  18. Feasibility of silver doped TiO2/glass fiber photocatalyst under visible irradiation as an indoor air germicide.

    PubMed

    Pham, Thanh-Dong; Lee, Byeong-Kyu

    2014-03-20

    This study investigated the feasibility of using Ag-TiO2 photocatalyst supported on glass fiber (Ag-TiO2/GF) prepared by a sol-gel method as an indoor air germicide. An experimental model was designed to investigate the bacterial disinfection efficiency of Staphylococcus (Staph), the most popular bacterium in hospitals in Korea, by the Ag-TiO2/GF photocatalyst. The silver content in Ag/TiO2 was altered from 1 to 10% to investigate the optimal ratio of Ag doped on TiO2/glass fiber (TiO2/GF) for photocatalytic disinfection of Staph. This study confirmed that Ag in Ag-TiO2/GF could work as an electron sink or donor to increase photocatalytic activity and promote the charge separation of electron-hole pairs generated from TiO2 after photon absorption. Ag also acts as an intermediate agent for the transfer of photo-generated electrons from the valence band of TiO2 to an acceptor (O2 gas) to promote photo-oxidation processes. The photocatalytic disinfection activity of Ag-TiO2/GF under visible light increased with the increase in silver content up to 7.5% and then slightly decreased with further increasing silver content. The highest disinfection efficiency and disinfection capacity of Staph using 7.5% Ag-TiO2/GF were 75.23% and 20 (CFU∙s-1∙cm-2) respectively. The medium level of humidity of 60% ± 5% showed better photocatalytic disinfection than the lower (40% ± 5%) or higher (80% ± 5%) levels.

  19. Measurements of KrF laser-induced O2 fluorescence in high-temperature atmospheric air

    NASA Technical Reports Server (NTRS)

    Grinstead, Jay H.; Laufer, Gabriel; Mcdaniel, James C., Jr.

    1993-01-01

    Conditions for obtaining laser-induced O2 fluorescence using a tunable KrF laser has been determined theoretically and experimentally. With this laser source, O2 rotational temperature measurement is possible even in the absence of vibrational equilibrium. Temperature measurement using a two-line excitation scheme has been demonstrated in a high-temperature atmospheric-air furnace. A measurement uncertainty of 10.7 percent for the temperature range 1325-1725 K was realized. At atmospheric pressure, O2 LIF measurements are possible for air temperatures above 1250 K. Interference from OH fluorescence in reacting flows can be avoided by the proper selection of O2 transitions. Depletion of the ground state population by the incident laser is negligible for intensities below 7.5 x 10 to the 6th W/sq cm/per cm.

  20. Hierarchically structured TiO2/PAN nanofibrous membranes for high-efficiency air filtration and toluene degradation.

    PubMed

    Su, Jiafei; Yang, Guohong; Cheng, Cuilian; Huang, Chen; Xu, He; Ke, Qinfei

    2017-12-01

    Hierarchically structured, nanoparticle-on-nanofiber composite membranes were successfully prepared by electrospray of titanium dioxide (TiO2) suspensions and electrospinning of polyacrylonitrile (PAN) solution simultaneously. The results showed that the TiO2 nanoparticles were highly dispersed on the surface of PAN nanofibers to construct hierarchical nanostructures, which could not only endow the composite membrane with high photocatalytic activity but also further improve the filter efficiency of the composite membrane. Furthermore, the photocatalytic activities and filter efficiencies of composite membranes could be further tuned by controlling the TiO2/PAN mass ratios. Our study indicated that the combination of TiO2 nanoparticles and PAN nanofibers via simultaneous electrospinning-spray offers a new strategy to construct advanced multifunctional TiO2/PAN membranes with hierarchical nanostructures, which could not only perform well in decomposing toluene but also remove particulate matter in air effectively. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Ultraviolet Excimer Laser-Based Ignition of H2/Air and H2/O2 Premixed Flows

    DTIC Science & Technology

    1990-08-01

    minimum occurring for lean mixtures. The ignition is due to efficient formation of microplasmas . Unlike the laser-produced microplasmas that are formed...Air Ignition by the ArF Excimer Lasero... ... .o.2 B. Microplasma Formation Mechanism ....... o...... ..... .o.o....2 C. Atmospheric Absorption...Ratio for H2/02 Premixed Flows Using ArF Laser (193 nm) (Unstable Resonator) ............... 3 2 Excitation Spectra for Microplasma Formation in H2

  2. Carnation-like MnO2 modified activated carbon air cathode improve power generation in microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Zhang, Peng; Li, Kexun; Liu, Xianhua

    2014-10-01

    Highly active and low-cost electrocatalysts are of great importance for large-scale commercial applications of microbial fuel cells (MFCs). In this work, we prepared an activated carbon (AC) air cathode containing electrodeposited γ-MnO2 using a potentiostatic method. The results indicated that carnation-like MnO2 crystals were bound to the surface of the AC air cathode after a deposition time of 10 min, which greatly improved the performance of the cathode. BET analysis results demonstrated that the electrodeposition of MnO2 decreased the micropore surface area of the cathode but increased the mesopore surface area. When compared with a bare AC air cathode, the electrodeposited MnO2 cathode exhibited higher catalytic activity for oxygen reduction reaction. The maximum power density of the MFC equipped with the electrodeposited MnO2 AC air cathode was 1554 mW m-2, which is 1.5 times higher than the control cathode.

  3. Synergistic influence of inorganic oxides (ZrO2 and SiO2) with N2H4 to protect composite coatings obtained via plasma electrolyte oxidation on Mg alloy.

    PubMed

    Zoubi, Wail Al; Kamil, Muhammad Prisla; Ko, Young Gun

    2017-01-18

    Different electrochemical approaches were proposed in this study to introduce nanoparticles to the coating layers, aiming at their in situ incorporation into the coating layers fabricated via plasma electrolytic oxidation (PEO). The addition of nanoparticles to the coating layers provided an electrochemical pathway to generate the functionalized coatings with a wide range of compositions and constituent phases as well giving the appearance of sealing the pores. In this study, the microstructure, chemical composition, and electrochemical response of the composite coating formed via one-stage PEO were compared with those obtained by means of structural modification of PEO coatings together with either impregnation or pre-deposition. For the combination of PEO and pre-deposition, the coating layer demonstrated less porous and better corrosion performance in the conditions used in this study, which were attributed to the denser and/or thicker layer resulting after incorporating the nanoparticles, such as SiO2 and ZrO2. In these methods, the nanoparticles were detected mainly not only near the coating surface, but also within the micro-defects inside the coating layers. Accordingly, the electrochemical analysis based on potentiodynamic polarization tests in 3.5 wt% NaCl solution clearly showed that the corrosion resistance of Mg alloy would be enhanced significantly due to the incorporation of SiO2 and ZrO2 or ZrO2 nanoparticles.

  4. Highly dispersed platinum nanoparticles on TiO2 prepared by using the microwave-assisted deposition method: an efficient photocatalyst for the formation of H2 and N2 from aqueous NH3.

    PubMed

    Fuku, Kojirou; Kamegawa, Takashi; Mori, Kohsuke; Yamashita, Hiromi

    2012-06-01

    A simple and practical technique to synthesize nanosized platinum particles loaded on TiO(2) (Pt-TiO(2)) by using a microwave (Mw)-assisted deposition method has been exploited in the development of a highly efficient photocatalyst for the formation of H(2) and N(2) gases from harmful nitrogen-containing chemical wastes, for example, aqueous ammonia (NH(3)). Upon Mw irradiation, a platinum precursor can be deposited quickly on the TiO(2) surface from an aqueous solution of platinum and subsequent reduction with H(2) affords the nanosized platinum metal particles with a narrow size distribution (Mw-Pt-TiO(2)). Characterization by CO adsorption, platinum L(III)-edge X-ray absorption fine structure analysis, and TEM analysis revealed that the size of the metal nanoparticles strongly depended on the preparation methods. Smaller platinum nanoparticles were obtained by the Mw heating method than those obtained by conventional preparation techniques, such as photoassisted deposition (PAD), impregnation (Imp), and equilibrium adsorption (EA) deposition by conventional convective heating. The H(2) and N(2) formation rates increased with increasing dispersity of platinum. Pt-TiO(2) prepared by the Mw heating method exhibited a specifically high H(2) formation activity in the photocatalytic decomposition of aqueous NH(3) in a nearly stoichiometric 3:1 (H(2)/N(2)) molar ratio under inert conditions. The present Mw heating method is applicable to a variety of anatase-type TiO(2) species possessing different specific surface areas to provide small and highly dispersed platinum nanoparticles with a narrow size distribution.

  5. Experimental and modeling study on effects of N2 and CO2 on ignition characteristics of methane/air mixture

    PubMed Central

    Zeng, Wen; Ma, Hongan; Liang, Yuntao; Hu, Erjiang

    2014-01-01

    The ignition delay times of methane/air mixture diluted by N2 and CO2 were experimentally measured in a chemical shock tube. The experiments were performed over the temperature range of 1300–2100 K, pressure range of 0.1–1.0 MPa, equivalence ratio range of 0.5–2.0 and for the dilution coefficients of 0%, 20% and 50%. The results suggest that a linear relationship exists between the reciprocal of temperature and the logarithm of the ignition delay times. Meanwhile, with ignition temperature and pressure increasing, the measured ignition delay times of methane/air mixture are decreasing. Furthermore, an increase in the dilution coefficient of N2 or CO2 results in increasing ignition delays and the inhibition effect of CO2 on methane/air mixture ignition is stronger than that of N2. Simulated ignition delays of methane/air mixture using three kinetic models were compared to the experimental data. Results show that GRI_3.0 mechanism gives the best prediction on ignition delays of methane/air mixture and it was selected to identify the effects of N2 and CO2 on ignition delays and the key elementary reactions in the ignition chemistry of methane/air mixture. Comparisons of the calculated ignition delays with the experimental data of methane/air mixture diluted by N2 and CO2 show excellent agreement, and sensitivity coefficients of chain branching reactions which promote mixture ignition decrease with increasing dilution coefficient of N2 or CO2. PMID:25750753

  6. Novel TiO2/C3N4 Photocatalysts for Photocatalytic Reduction of CO2 and for Photocatalytic Decomposition of N2O.

    PubMed

    Reli, Martin; Huo, Pengwei; Šihor, Marcel; Ambrožová, Nela; Troppová, Ivana; Matějová, Lenka; Lang, Jaroslav; Svoboda, Ladislav; Kuśtrowski, Piotr; Ritz, Michal; Praus, Petr; Kočí, Kamila

    2016-11-03

    TiO2/g-C3N4 photocatalysts with the ratio of TiO2 to g-C3N4 ranging from 0.3/1 to 2/1 were prepared by simple mechanical mixing of pure g-C3N4 and commercial TiO2 Evonik P25. All the nanocomposites were characterized by X-ray powder diffraction, UV-vis diffuse reflectance spectroscopy, photoluminescence, X-ray photoelectron spectroscopy, Raman spectroscopy, infrared spectroscopy, transmission electron microscopy, photoelectrochemical measurements, and nitrogen physisorption. The prepared mixtures along with pure TiO2 and g-C3N4 were tested for the photocatalytic reduction of carbon dioxide and photocatalytic decomposition of nitrous oxide. The pure g-C3N4 exhibited the lowest photocatalytic activity in both cases, pointing to a very high recombination rate of charge carriers. On the other hand, the most active photocatalyst toward all the products was (0.3/1)TiO2/g-C3N4. The highest activity is achieved by combination of a number of factors: (i) specific surface area, (ii) adsorption edge energy, (iii) crystallite size, and (iv) efficient separation of the charge carriers, where the efficient charge separation is the most decisive parameter.

  7. Characteristics of dye-sensitized solar cell with TiO2 anode under UV irradiation

    NASA Astrophysics Data System (ADS)

    Lee, Ming-Kwei; Hsiao, Chih-Chen; Weng, Hao-Wei

    2016-03-01

    The anatase phase crystalline quality of commercial TiO2 (P25) nanoparticle sintered in air and N2 is improved. Compared DSSC with air-sintered TiO2 anode, DSSC with N2-sintered TiO2 anode has better performance mainly from high optical absorption efficiency. Under UV irradiation, organic contaminants adsorbed on TiO2 are dissociated by the photocatalysis, and the dye adsorption is enhanced. The DSSC performance with UV-treated/N2-sintered TiO2 anode is further improved.

  8. Decomposition of benzene and toluene in air streams in fixed-film photoreactors coated with TiO2 catalyst.

    PubMed

    Ku, Young; Chen, Juan-Shiang; Chen, Hua-Wei

    2007-03-01

    The decomposition of benzene and toluene in air streams by UV/TiO2 process was studied in different annular photoreactors under various operating conditions. The shells of reactors used in this research are made of stainless steel, Pyrex glass, or titanium. The TiO2 film was coated to the inner surface of the reactors by either rotating coating or sol-gel techniques. The TiO2 films coated by sol-gel technique were found to be smoother and more uniform than those coated by rotating coating. However, experimental results indicated that the photocatalysis of benzene or toluene in a glass reactor with rotating-coated TiO2 film delivered higher decompositions in air streams than that with sol-gel coated reactors. Benzene and toluene were decomposed more effectively in a coated glass reactor than in a coated stainless steel reactor under the same operating conditions. The presence of water vapor in air-stream plays an important role in the decomposition of benzene and toluene, and a relative humidity of approximately 5-6% was found to be adequate. The presence of excessive amounts of humidity retarded the decomposition to certain extents possibly results from the competitive adsorption of water molecules on the active sites of TiO2.

  9. Rotational Temperature and Number Density Measurements of N2, O2, CO, and CO2 in a Hypersonic Flow Field Using Laser-Raman Spectroscopy

    DTIC Science & Technology

    1975-07-01

    SPECTROSCOPY , , VON KARMAN GAS DYNAMICS FACILITY ARNOLD ENGINEERING DEVELOPMENT CENTER AIR FORCE SYSTEMS COMMAND ARNOLD AIR FORCE STATION, TENNESSEE 37389 July...LIDRARY - ARNOLD AfB t TN 37339 Prepared for DIRECTORATE OF TECHNOLOGY ARNOLD ENGINEERING DEVELOPMENT CENTER ARNOLD AIR FORCE STATION, TENNESSEE...wORK UNIT NUMBERS Arnold Engineering Development Center (DY) Program Element Arnold Air Force Station, Tennessee 37389 65802F 11. CONTROLLING OFFICE

  10. A computational study of hydrogen bonds in intermolecular systems of high complexity: arachno-pentaborane(11)···Y with Y = O2 and N 2.

    PubMed

    Zabardasti, Abedin; Goudarziafshar, Hamid; Salehnassaj, Maryam; Oliveira, Boaz G

    2014-09-01

    The interactions of arachno-B(5)H(11) with N(2) and O(2) were theoretically studied. In the B(5)H(11)···N(2) and B(5)H(11)···O(2) complexes, the terminal hydrogens of B(5)H(11) work as electron donors whereas the bridge ones as electron acceptors. The optimized structures and the corresponding harmonic vibration spectra were investigated through the MP2/aug-cc-pVDZ level of theory. In order to characterize the hydrogen bonds, the topological calculations inherent to the QTAIM protocol and MEP analysis were carried out. The NBO analyses were useful in the interpretation of the red-shifts and blue-shifts on the stretch frequencies of the proton donors, of course in agreement with the Bent rule for the chemical bonding as well as by the conceptions of hyperconjugation or hybridization.

  11. Efficiency of clay-TiO2 nanocomposites on the photocatalytic eliminationof a model hydrophobic air pollutant

    SciTech Connect

    Kibanova, Daria; Cervini-Silva, Javiera; Destaillats, Hugo

    2009-01-01

    Clay-supported TiO2 photocatalysts can potentially improve the performance of air treatment technologies via enhanced adsorption and reactivity of target volatile organic compounds (VOCs). In this study, a bench-top photocatalytic flow reactor was used to evaluate the efficiency of hectorite-TiO2 and kaolinite-TiO2, two novel composite materials synthesized in our laboratory. Toluene, a model hydrophobic VOC and a common indoor air pollutant, was introduced in the air stream at realistic concentrations, and reacted under UVA (gamma max = 365 nm) or UVC (gamma max = 254 nm) irradiation. The UVC lamp generated secondary emission at 185 nm, leading to the formation of ozone and other short-lived reactive species. Performance of clay-TiO2 composites was compared with that of pure TiO2 (Degussa P25), and with UV irradiation in the absence of photocatalyst under identical conditions. Films of clay-TiO2 composites and of P25 were prepared by a dip-coating method on the surface of Raschig rings, which were placed inside the flow reactor. An upstream toluene concentration of ~;;170 ppbv was generated by diluting a constant flow of toluene vapor from a diffusion source with dry air, or with humid air at 10, 33 and 66percent relative humidity (RH). Toluene concentrations were determined by collecting Tenax-TA (R) sorbent tubes downstream of the reactor, with subsequent thermal desorption -- GC/MS analysis. The fraction of toluene removed, percentR, and the reaction rate, Tr, were calculated for each experimental condition from the concentration changes measured with and without UV irradiation. Use of UVC light (UV/TiO2/O3) led to overall higher reactivity, which can be partially attributed to the contribution of gas phase reactions by short-lived radical species. When the reaction rate was normalized to the light irradiance, Tr/I gamma, the UV/TiO2 reaction under UVA irradiation was more efficient for samples with a higher content of TiO2 (P25 and Hecto-TiO2), but not for Kao-TiO

  12. Constraining N2O emissions over the last century by firn air isotope measurements in both hemispheres

    NASA Astrophysics Data System (ADS)

    Prokopiou, Markella; Sapart, Celia; Martinerie, Patricia; Witrant, Emmanuel; Ishijima, Kentaro; Magand, Sophie; Kaiser, Jan; van de Wal, Roderik; Röckmann, Thomas

    2014-05-01

    N2O is a greenhouse gas that it is responsible for increased radiative forcing of the climate system. In addition to this, it is primarily destroyed in the stratosphere providing an important source of NOx, which in turn plays an important role in ozone depletion. Large uncertainties remain as to the actual strength of the individual sources of N2O. Knowledge of the historical record, of the temporal evolution of N2O emissions, can provide insight on how its sources and sinks altered during the industrial period. Data from air trapped in firn enables us to better determine the source/sink strength emissions over time. In this study we analyze firn measurements on 15N, 18O and position dependent 15N isotopic composition of N2O, from both hemispheres, combining new and previously published data, in order to constrain the N2O budget. From the Northern Hemisphere we use data from North Greenland Ice core Project (NGRIP) and North Eemian Ice core Project (NEEM) and for the Southern Hemisphere we use data from Berkner Island (BI), Dronning Maud Land (DML) and Dome Concordia (DOME C). Results show that the isotopic composition of 15N, 18O of N2O is presently more depleted which indicates a strong depleting source contribution probably originating from agricultural activities. The LGGE-GIPSA firn air diffusion model allows single site reconstructions, as well as using all data together in a multi-site inversion, in order to reconstruct the temporal evolution of N2O and its isotopic composition. We investigate the consistency between the different datasets and present a best-guess isotope history based on the firn air data. A simple two-box atmospheric model is applied in order to simulate the N2O atmospheric contribution from different sources and sinks.

  13. Quantitative absorption spectroscopy of residual water vapor in high-purity gases: pressure broadening of the 1.39253-microm H2O transition by N2, HCl, HBr, Cl2, and O2.

    PubMed

    Vorsa, Vasil; Dheandhanoo, Seksan; Ketkar, Suhas N; Hodges, Joseph T

    2005-02-01

    We determined the respective pressure-broadening coefficients of HCl, HBr, Cl2, and O2 (expressed relative to that of the reference gas N2) for the (v1,v2,v3)J(Ka,Kc) = (0,0,0)3(0,3) --> (1,0,1)2(0,2) rovibrational transition of H2 16O that occurs at 1.39253 microm. The experiment used a continuous-wave cavity ring-down spectroscopy analyzer to measure the peak absorption losses as a function of added moisture concentration. The measured pressure-broadening coefficients for HCl, HBr, Cl2, and O2 are, respectively, 2.76, 2.48, 1.39, and 0.49 times that of the N2 pressure-broadening coefficient, and detection limits for water vapor range from 0.22 nmol mol(-1) for O2 matrix gas to 2.3 nmol mol(-1) for HBr matrix gas. The degradation of the detection limit (relative to the N2 matrix gas) is ascribed to a pressure-broadening-induced reduction in peak absorption cross section and to elevated background loss from the matrix gas.

  14. The Role of Air-Electrode Structure on the Incorporation of Immiscible PFCs in Nonaqueous Li-O2 Battery.

    PubMed

    Balaish, Moran; Ein-Eli, Yair

    2017-03-22

    Perfluorocarbons (PFCs) are considered advantageous additives to nonaqueous Li-O2 battery due to their superior oxygen solubility and diffusivity compared to common battery electrolytes. Up to now, the main focus was concentrated on PFCs-electrolyte investigation; however, no special attention was granted to the role of carbon structure in the PFCs-Li-O2 system. In our current research, immiscible PFCs, rather than miscible fluorinated ethers, were added to activated carbon class air electrode due to their higher susceptibility toward O2(•-) attack and to their ability to shift the reaction from two-phase to an artificial three-phase reaction zone. The results showed superior battery performance upon PFCs addition at lower current density (0.05 mA cm(-2)) but unexpectedly failed to do so at higher current density (0.1 and 0.2 mA cm(-2)), where oxygen transport limitation is best illustrated. The last was a direct result of liquid-liquid displacement phenomenon occurring when the two immiscible liquids were introduced into the porous carbon medium. The investigation and role of carbon structure on the mechanism upon PFCs addition to Li-O2 system are suggested based on electrochemical characterization, wettability behavior studies, and the physical adsorption technique. Finally, we suggest an optimum air-electrode structure enabling the incorporation of immiscible PFCs in a nonaqueous Li-O2 battery.

  15. Comparison of Benzene & Toluene removal from synthetic polluted air with use of Nano photocatalyticTiO2/ ZNO process

    PubMed Central

    2014-01-01

    Background Mono aromatic hydrocarbons (BTEX) are a group of hazardous pollutants which originate from sources such as refineries, gas, and oil extraction fields, petrochemicals and paint and glue industries. Conventional methods, including incineration, condensation, adsorption and absorption have been used for removal of VOCs. None of these methods is economical for removal of pollutants of polluted air with low to moderate concentrations. The heterogeneous photocatalytic processes involve the chemical reactions to convert pollutant to carbon dioxide and water. The aim of this paper is a comparison of Benzene & Toluene removal from synthetic polluted air using a Nano photocatalytic TiO2/ ZNO process. Results The X-ray diffraction (XRD) patterns showed that Nano crystals of TiO2 and ZNO were in anatase and rutile phases. Toluene & benzene were decomposed by TiO2/ ZNO Nano photocatalyst and UV radiation. Kruskal-wallis Test demonstrated that there are significant differences (pvalue < 0.05) between pollutant concentrations in different operational conditions. Conclusions Degradation of toluene & benzene increases with increasing UV intensity and decreasing initial concentrations. Effect of TiO2/ZNO Nano photocatalyst on benzene is less than that on toluene. In this research, Toluene & benzene removal by TiO2/ZNO and UV followed first-order reactions. PMID:24499601

  16. Interaction between air plasma-produced aqueous 1O2 and the spin trap DMPO in electron spin resonance

    NASA Astrophysics Data System (ADS)

    Chen, Chen; Li, Fanying; Chen, Hai-Lan; Kong, Michael G.

    2017-10-01

    A series of electron spin resonance (ESR) experiments is done to quantitatively measure the concentrations of aqueous 1O2 and ˙OH produced by a surface micro-discharge air plasma device. 1O2 is tested to be existed in the plasma treated solution by using the spin trap of TEMP. However, the unexpected DMPOX spectrum is observed in measuring ˙OH by the spin trap of 5,5-Dimethyl-1-Pyrroline-N-Oxide (DMPO). With more chemical scavenger experiments, it is found that removal of aqueous 1O2 leads to the disappearance of DMPOX in ESR. Therefore, the generation of DMPOX is directly related to the oxidation of DMPO by plasma-produced aqueous 1O2. This oxidation process and interactions between DMPO and chemical scavengers used in experiments can all be well explained by a proposed reaction mechanism. The revelation of interactions between aqueous 1O2 and the spin trap DMPO shows that the observation of spectra of DMPOX in the ESR measurement can be regarded as a marker of high concentrations of plasma-produced 1O2 in liquid. These results also prove the existence of interactions between spin traps and non-targeted plasma-produced reactive species in ESR experiments. Also, these results have offered a better understanding of the use of spin traps such as DMPO in the plasma-induced highly oxidative aqueous environment.

  17. A novel thermally stable hydroperoxo-copper(II) complex in a Cu(N2O2) chromophore of a potential N4O2 donor Schiff base ligand: synthesis, structure and catalytic studies.

    PubMed

    Biswas, Surajit; Dutta, Arpan; Debnath, Mainak; Dolai, Malay; Das, Kalyan K; Ali, Mahammad

    2013-09-28

    The generation and study of metal-hydroperoxo/metal-peroxo (LCu(II)-OOH or LCu(II)-OO˙) complexes is a fascinating area of research of many chemical and biochemical researchers, because of their involvement as active intermediates in many biological and industrial catalytic oxidation processes. For this purpose we have designed a bulky hexa-coordinating ligand with potential N4O2 donor atoms which could provide an opportunity to synthesize a mononuclear Cu(II) complex with an aim to utilize it in the catalytic oxidation of aromatic hydrocarbons by an environmentally benign oxidant, H2O2. The Cu(II) complex (1) was structurally characterized and found to have square-planar geometry with the two pyrazolyl groups remaining in dangling mode. A novel mononuclear complex [Et3NH][LCu(II)-OOH] (2) was found to form in the reaction between 1 and H2O2 in the presence of Et3N. The presence of this dangling groups favours the stability of hydroperoxo species, [LCu-OOH](-) (2) through H-bonding with the coordinated phenoxo oxygen atom, which was confirmed by ESI-MS(+) and MS(-) (m/z) mass analysis and DFT calculations. This complex was found to be thermally stable at room temperature [k(d) = (5.67 ± 0.03) × 10(-5) s(-1) at 25 °C] and may be due to the formation of O-O-H···O(phenoxo) H-bonding as delineated by the DFT calculations. Complex 1 was found to be an efficient catalyst for the oxidation of aromatic hydrocarbons to the corresponding aldehyde and alcohol in 2:1 mole ratio with TON ~300.

  18. Synthesis of Cu/TiO2/organo-attapulgite fiber nanocomposite and its photocatalytic activity for degradation of acetone in air

    NASA Astrophysics Data System (ADS)

    Zhang, Gaoke; Wang, He; Guo, Sheng; Wang, Junting; Liu, Jin

    2016-01-01

    The Cu/TiO2/organo-attapulgite fiber (CTOA) nanocomposite was synthesized by a facile method and was used for photocatalytic degradation of acetone in air under UV light irradiation. The as-prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscope (SEM), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectrum (UV-vis DRS), inductively coupled plasma (ICP) spectrometry and N2 adsorption-desorption measurement. The results showed that the structure of organo-attapulgite (OAT) had no obvious change as compared to unmodified attapulgite (AT) and the attapulgite fibers in the OAT were well-dispersed. Both micropores and mesopores exist in the CTOA catalyst. The CTOA catalysts prepared at the Cu/TiO2 molar ratio of 0.003 shows an excellent photocatalytic activity for the degradation of acetone in air. The synergistic effect of Cu species and cetyltrimethylammonium bromide modification can be responsible for the enhanced photocatalytic activity of the CTOA catalyst. The mechanism of the photocatalytic degradation of acetone by the CTOA catalyst was discussed.

  19. Improved Wetting Characteristics in TiO2–Modified Ag-CuO Air Braze Filler Metals

    SciTech Connect

    Weil, K. Scott; Kim, Jin Yong Y.; Hardy, John S.; Darsell, Jens T.

    2006-01-01

    In this paper we report on the results of a series of sessile drop experiments designed to examine the effect of TiO2 on the wetting behavior of Ag-CuO air braze filler metals. It was found that TiO2 concentrations as small as 0.5 mol% can significantly decrease the contact angle of Ag-CuO on alumina over a compositional range of 1 – 34mol% CuO. The effect appears to maximize at a copper oxide concentration of ~4 mol% CuO regardless of the titania content.

  20. Effect of CuO2 planes on the structural and superconducting transport properties of [CuTl - 12(n - 1)n;n = 2,3,4] superconductor family

    NASA Astrophysics Data System (ADS)

    Muzaffar, M. Usman; Khan, Nawazish A.

    2016-06-01

    Cu0.5Tl0.5Ba2Can-1CunO2n+4-δ (n = 2, 3, 4) superconducting bulk samples have been synthesized by using two-step solid state reaction method. We investigated the effects of CuO2 planes on the structural and superconducting transport properties of [CuTl - 12(n - 1)n; n = 2, 3, 4] superconducting family. These samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) absorption spectroscopy and DC-resistivity (ρ) measurements. These samples are c-axis length oriented and have shown orthorhombic crystal structure. All the samples have shown metallic variations of resistivity from room temperature down to onset of superconductivity. The zero resistivity critical temperature Tc(R = 0) increases with the increase in superconducting planes and normal state resistivity systematically decreases, which show the density of inadvertent defects decreases in the final compound. The apical oxygen phonon modes are hardened as observed in the FTIR absorption measurements. The intrinsic microscopic superconducting parameters, such as the cross-over temperatures, coherence length along c-axis (ξc(0)) at 0 K, inter-layer coupling (J), inter-grain coupling (α) and fermi velocity (VF), were extracted from the fluctuation-induced conductivity (FIC) analysis. FIC analysis also showed the improvement in superconductivity with the increase in CuO2 planes.

  1. Nanoscale mechanochemical wear of phosphate laser glass against a CeO2 particle in humid air

    NASA Astrophysics Data System (ADS)

    Yu, Jiaxin; He, Hongtu; Zhang, Yafeng; Hu, Hailong

    2017-01-01

    Using an atomic force microscope, the friction and wear of phosphate laser glass against a CeO2 particle were quantitatively studied both in humid air and in vacuum, to reveal the water molecules induced mechanochemical wear mechanism of phosphate laser glass. The friction coefficient of the glass/CeO2 pair in air was found to be 5-7 times higher than that in vacuum due to the formation of a capillary water bridge at the friction interface, with a contribution of the capillary-related friction to the total friction coefficient as high as 65-79%. The capillary water bridge further induced a serious material removal of glass and CeO2 particle surfaces, while supplying both a local liquid water environment to corrode the glass surface and a high shearing force to assist the stretching of the Cesbnd Osbnd P bond, accelerating the reaction between water and the glass/CeO2 pair. In vacuum, however, no discernable wear phenomena were observed, but the phase images captured by AFM tapping mode suggested the occurrence of potential strain hardening in the friction area of the glass surface.

  2. Structural and Electrical Characterization of SiO2 Gate Dielectrics Deposited from Solutions at Moderate Temperatures in Air.

    PubMed

    Esro, Mazran; Kolosov, Oleg; Jones, Peter J; Milne, William I; Adamopoulos, George

    2017-01-11

    Silicon dioxide (SiO2) is the most widely used dielectric for electronic applications. It is usually produced by thermal oxidation of silicon or by using a wide range of vacuum-based techniques. By default, the growth of SiO2 by thermal oxidation of silicon requires the use of Si substrates whereas the other deposition techniques either produce low quality or poor interface material and mostly require high deposition or annealing temperatures. Recent investigations therefore have focused on the development of alternative deposition paradigms based on solutions. Here, we report the deposition of SiO2 thin film dielectrics deposited by spray pyrolysis in air at moderate temperatures of ≈350 °C from pentane-2,4-dione solutions of SiCl4. SiO2 dielectrics were investigated by means of UV-vis absorption spectroscopy, spectroscopic ellipsometry, XPS, XRD, UFM/AFM, admittance spectroscopy, and field-effect measurements. Data analysis reveals smooth (RRMS < 1 nm) amorphous films with a dielectric constant of about 3.8, an optical band gap of ≈8.1 eV, leakage current densities in the order of ≈10(-7) A/cm(2) at 1 MV/cm, and high dielectric strength in excess of 5 MV/cm. XPS measurements confirm the SiO2 stoichiometry and FTIR spectra reveal features related to SiO2 only. Thin film transistors implementing spray-coated SiO2 gate dielectrics and C60 and pentacene semiconducting channels exhibit excellent transport characteristics, i.e., negligible hysteresis, low leakage currents, high on/off current modulation ratio on the order of 10(6), and high carrier mobility.

  3. Optimal frequency selection of multi-channel O2-band different absorption barometric radar for air pressure measurements

    NASA Astrophysics Data System (ADS)

    Lin, Bing; Min, Qilong

    2017-02-01

    Through theoretical analysis, optimal selection of frequencies for O2 differential absorption radar systems on air pressure field measurements is achieved. The required differential absorption optical depth between a radar frequency pair is 0.5. With this required value and other considerations on water vapor absorption and the contamination of radio wave transmission, frequency pairs of present considered radar system are obtained. Significant impacts on general design of differential absorption remote sensing systems are expected from current results.

  4. Porous TiO2 microspheres with tunable properties for photocatalytic air purification.

    PubMed

    Naldoni, Alberto; Bianchi, Claudia L; Pirola, Carlo; Suslick, Kenneth S

    2013-01-01

    The synthesis of highly-crystalline porous TiO(2) microspheres is reported using ultrasonic spray pyrolysis (USP) in the presence of colloidal silica as a template. We have exploited the interactions between hot SiO(2) template particles surface and TiO(2) precursor that occur during reaction inside the droplets, to control the physical and chemical properties of the resulting particles. Varying the SiO(2) to titanium precursor molar ratio and the colloidal silica dimension, we obtained porous titania microspheres with tunable morphology, porosity, BET surface area, crystallite size, band-gap, and phase composition. In this regard, we have also observed the preferential formation of anatase vs. rutile with increasing initial surface area of the silica template. The porous TiO(2) microspheres were tested in the photocatalytic degradation of nitrogen oxides (NO(x)) in the gas phase. USP prepared nanostructured titania samples were found to have significantly superior specific activity per surface area compared to a commercial reference sample (P25 by Evonik-Degussa). Copyright © 2012 Elsevier B.V. All rights reserved.

  5. Terrestrial biospheric and oceanic CO2 uptakes estimated from long-term measurements of atmospheric CO2 mole fraction, δ13C, and δ(O2/N2) at Ny-Ålesund, Svalbard

    NASA Astrophysics Data System (ADS)

    Goto, Daisuke; Morimoto, Shinji; Ishidoya, Shigeyuki; Aoki, Shuji; Nakazawa, Takakiyo

    2017-05-01

    Systematic observations of CO2 mole fraction, the isotopic ratio δ13C of CO2, and oxygen to nitrogen ratio (δ(O2/N2)) in the atmosphere have been carried out at Ny-Ålesund, Svalbard, since 1991, 1996, and 2001, respectively. The CO2 mole fraction shows a clear seasonal cycle superimposed on a secular increase with an average rate of 2.0 ppm yr-1 for the period of 1996-2013. On the other hand, δ13C and δ(O2/N2) decrease secularly at an average rate of -0.020‰ yr-1 for 1996-2013 and -19.9 per meg yr-1 for 2001-2013, respectively. Based on the observed secular trends of the CO2 mole fraction and δ(O2/N2), the average CO2 uptake during 2001-2013 was estimated to be 1.6 ± 0.8 and 2.3 ± 0.5 GtC yr-1 for the terrestrial biosphere and the ocean, respectively. By using the observed CO2 and δ13C, the corresponding CO2 uptakes of 1.3 ± 0.6 and 2.6 ± 0.5 GtC yr-1 were obtained for the same period. The estimates from the two methods are in good agreement with each other. The terrestrial biospheric CO2 uptake derived by the latter method showed large interannual variability in association with El Niño events. On the other hand, the oceanic uptake increased secularly with less interannual variability during 1996-2013.

  6. Development of automated preparation system for isotopocule analysis of N2O in various air samples

    NASA Astrophysics Data System (ADS)

    Toyoda, Sakae; Yoshida, Naohiro

    2016-05-01

    Nitrous oxide (N2O), an increasingly abundant greenhouse gas in the atmosphere, is the most important stratospheric ozone-depleting gas of this century. Natural abundance ratios of isotopocules of N2O, NNO molecules substituted with stable isotopes of nitrogen and oxygen, are a promising index of various sources or production pathways of N2O and of its sink or decomposition pathways. Several automated methods have been reported to improve the analytical precision for the isotopocule ratio of atmospheric N2O and to reduce the labor necessary for complicated sample preparation procedures related to mass spectrometric analysis. However, no method accommodates flask samples with limited volume or pressure. Here we present an automated preconcentration system which offers flexibility with respect to the available gas volume, pressure, and N2O concentration. The shortest processing time for a single analysis of typical atmospheric sample is 40 min. Precision values of isotopocule ratio analysis are < 0.1 ‰ for δ15Nbulk (average abundances of 14N15N16O and 15N14N16O relative to 14N14N16O), < 0.2 ‰ for δ18O (relative abundance of 14N14N18O), and < 0.5 ‰ for site preference (SP; difference between relative abundance of 14N15N16O and 15N14N16O). This precision is comparable to that of other automated systems, but better than that of our previously reported manual measurement system.

  7. Differential cross sections for scattering of 0.5-, 1.5-, and 5.0-keV hydrogen atoms by He, H2, N2, and O2

    NASA Technical Reports Server (NTRS)

    Newman, J. H.; Chen, Y. S.; Smith, K. A.; Stebbings, R. F.

    1986-01-01

    This paper reports measurements of absolute cross sections, differential in angle, for scattering of 0.5-, 1.5-, and 5.0-keV hydrogen atoms by He, H2, N2, and O2 at laboratory scattering angles between 0.1 and 5 deg. The measured cross sections are the sums of those for elastic and inelastic collisions having a fast H atom product and are needed for calculating energy transfer to the upper atmosphere from precipitating ring current particles.

  8. Palladium(II) and zinc(II) complexes of neutral [N2O2] donor Schiff bases derived from furfuraldehyde: synthesis, characterization, fluorescence and corrosion inhibitors of ligands.

    PubMed

    Ali, Omyma A M

    2014-11-11

    Metal complexes of Schiff bases derived from furfuraldehyde and 4,5-dimethyl-1,2-phenylendiamine (L1) or 4,5-dichloro-1,2-phenylendiamine (L2) have been reported and characterized based on elemental analyses, IR, 1H NMR, UV-Vis, magnetic moment, molar conductance and thermal analysis. The complexes are found to have the formulae [PdL1-2]Cl2 and [ZnL1-2](AcO)2·H2O. The molar conductance data reveal that Pd(II) and Zn(II) chelates are ionic in nature and are of the type 2:1 electrolytes. The spectral data are consistent with a square planar and tetrahedral geometry around Pd(II) and Zn(II), respectively, in which the ligands act as tetradentate ligands. The thermal behavior of some chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The corrosion inhibition of stainless steel types 410 and 304 in 1 M HCl using the synthesized Schiff bases as inhibitors have been studied by weight loss method. The obtained data considered these ligands as efficient corrosion inhibitors. The ligands and their metal complexes exhibited considerable antibacterial activity against Staphylococcusaureus, and Escherichiacoli and antifungal activity against Candida albicans. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Palladium(II) and zinc(II) complexes of neutral [N2O2] donor Schiff bases derived from furfuraldehyde: Synthesis, characterization, fluorescence and corrosion inhibitors of ligands

    NASA Astrophysics Data System (ADS)

    Ali, Omyma A. M.

    2014-11-01

    Metal complexes of Schiff bases derived from furfuraldehyde and 4,5-dimethyl-1,2-phenylendiamine (L1) or 4,5-dichloro-1,2-phenylendiamine (L2) have been reported and characterized based on elemental analyses, IR, 1H NMR, UV-Vis, magnetic moment, molar conductance and thermal analysis. The complexes are found to have the formulae [PdL1-2]Cl2 and [ZnL1-2](AcO)2·H2O. The molar conductance data reveal that Pd(II) and Zn(II) chelates are ionic in nature and are of the type 2:1 electrolytes. The spectral data are consistent with a square planar and tetrahedral geometry around Pd(II) and Zn(II), respectively, in which the ligands act as tetradentate ligands. The thermal behavior of some chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The corrosion inhibition of stainless steel types 410 and 304 in 1 M HCl using the synthesized Schiff bases as inhibitors have been studied by weight loss method. The obtained data considered these ligands as efficient corrosion inhibitors. The ligands and their metal complexes exhibited considerable antibacterial activity against Staphylococcusaureus, and Escherichiacoli and antifungal activity against Candida albicans.

  10. Effect of fuel to air ratio on Mach 0.3 burner rig hot corrosion of ZrO2-Y2O3 thermal barrier coatings

    NASA Technical Reports Server (NTRS)

    Hodge, P. E.

    1982-01-01

    A Mach 0.3 burner rig test program was conducted to determine how the fuel to air mass ratio affects the durability of ZrO2-Y2O3/Ni-16Cr-6Al-0.31Y thermal barrier coating systems in combustion products containing 5 ppm Na and 2 ppm V. As the fuel to air mass ratio was increased from 0.039 to 0.049, the durability of ZrO2-6Y2O3, ZrO2-8Y2O3 and ZrO2-12Y2O3 coatings decreased. ZrO2-8Y2O3 coatings were approximately 2X and 1.3X more durable than ZrO2-12Y2O3 and ZrO2-6Y2O3 coatings respectively at the fuel to air mass ratio of 0.039. The number of one hour cycles endured by ZrO2-8Y2O3 coatings varied from averages of 53 to 200 for the fuel to air mass ratios of 0.049 and 0.039, respectively. At the fuel to air mass ratio of 0.049, all ZrO2-Y2O3 coated specimens failed in 40 to 60 one hour cycles

  11. Predicting solvent stability in aprotic electrolyte Li-air batteries: nucleophilic substitution by the superoxide anion radical (O2(•-)).

    PubMed

    Bryantsev, Vyacheslav S; Giordani, Vincent; Walker, Wesley; Blanco, Mario; Zecevic, Strahinja; Sasaki, Kenji; Uddin, Jasim; Addison, Dan; Chase, Gregory V

    2011-11-10

    There is increasing evidence that cyclic and linear carbonates, commonly used solvents in Li ion battery electrolytes, are unstable in the presence of superoxide and thus are not suitable for use in rechargeable Li-air batteries employing aprotic electrolytes. A detailed understanding of related decomposition mechanisms provides an important basis for the selection and design of stable electrolyte materials. In this article, we use density functional theory calculations with a Poisson-Boltzmann continuum solvent model to investigate the reactivity of several classes of aprotic solvents in nucleophilic substitution reactions with superoxide. We find that nucleophilic attack by O(2)(•-) at the O-alkyl carbon is a common mechanism of decomposition of organic carbonates, sulfonates, aliphatic carboxylic esters, lactones, phosphinates, phosphonates, phosphates, and sulfones. In contrast, nucleophilic reactions of O(2)(•-) with phenol esters of carboxylic acids and O-alkyl fluorinated aliphatic lactones proceed via attack at the carbonyl carbon. Chemical functionalities stable against nucleophilic substitution by superoxide include N-alkyl substituted amides, lactams, nitriles, and ethers. The results establish that solvent reactivity is strongly related to the basicity of the organic anion displaced in the reaction with superoxide. Theoretical calculations are complemented by cyclic voltammetry to study the electrochemical reversibility of the O(2)/O(2)(•-) couple containing tetrabutylammonium salt and GCMS measurements to monitor solvent stability in the presence of KO(2)(•) and a Li salt. These experimental methods provide efficient means for qualitatively screening solvent stability in Li-air batteries. A clear correlation between the computational and experimental results is established. The combination of theoretical and experimental techniques provides a powerful means for identifying and designing stable solvents for rechargeable Li-air batteries.

  12. Synthesis, characterization, EPR spectroscopy and catalytic activity of a new oxidovanadium(IV) complex with N2O2-donor ligand

    NASA Astrophysics Data System (ADS)

    Mahboubi-Anarjan, Parisa; Bikas, Rahman; Hosseini-Monfared, Hassan; Aleshkevych, Pavlo; Mayer, Peter

    2017-03-01

    A new oxidovanadium(IV) complex, 2[VOL(OH2)] CH3OH (1), was synthesized from the reaction of VO(acac)2 with a symmetric N,O-donor Schiff base ligand (H2L), in which H2L is 6,6'-((1E,1‧E)-((2-hydroxypropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene))bis(2-methoxyphenol). The compounds were characterized by elemental analysis and spectroscopic methods. The molecular structure of complex was determined by single-crystal X-ray analysis which indicated that the crystal packing of complex contains two independent mononuclear vanadium complexes connected together by several strong hydrogen bonding interactions. The EPR spectrum of powdered complex 1 at liquid helium temperature showed two intensive octets which proved to be associated with V4+ ions with 3d1 electronic configuration. From EPR spectrum the values of the parameters: g|| = 1.9454 ± 0.0004, g⊥ = 1.9491 ± 0.0004, A|| = 0.0084 ± 0.0008 cm-1 and A⊥ = 0.0033 ± 0.0006 cm-1 were calculated for this complex. Complex 1 was employed as catalyst for oxidation of cyclooctene in the presence of H2O2 as oxidant. In order to obtain the suitable condition of catalytic oxidation, the effect of various parameters including the amount of the catalyst, temperature and solvent was studied. The results of catalytic studies showed that complex 1 can provide an effective and selective catalytic system for epoxidation of cyclooctene.

  13. Effects of CO2/N2 dilution on laminar burning velocity of stoichiometric DME-air mixture at elevated temperatures.

    PubMed

    Mohammed, Abdul Naseer; Juhany, Khalid A; Kumar, Sudarshan; Kishore, V Ratna; Mohammad, Akram

    2017-03-21

    The laminar burning velocity of CO2/N2 diluted stoichiometric dimethyl ether (DME) air mixtures is determined experimentally at atmospheric pressure and elevated mixture temperatures using a mesoscale high aspect-ratio diverging channel with inlet dimensions of 25mm×2mm. In this method, planar flames at different initial temperatures (Tu) were stabilized inside the channel using an external electric heater. The magnitude of burning velocities was acquired by measuring the flame position and initial temperature. The mass conservation of the mixture entering the inlet and the stationary planar flame front is applied to obtain the laminar burning velocity. Laminar burning velocity at different initial mixture temperatures is plotted with temperature ratio (Tu/Tu,o), where a reference temperature (Tu,o) of 300K is used. Enhancement in the laminar burning velocity is observed with mixture temperature for DME-air mixtures with CO2 and N2 dilutions. A significant decrease in the burning velocity and slight increase in temperature exponent of the stoichiometric DME-air mixture was observed with dilution at same temperatures. The addition of CO2 has profound influence when compared to N2 addition on both burning velocity and temperature exponent.

  14. Highly efficient photocatalytic TiO2 coatings deposited by open air atmospheric pressure plasma jet with aerosolized TTIP precursor

    NASA Astrophysics Data System (ADS)

    Fakhouri, H.; Ben Salem, D.; Carton, O.; Pulpytel, J.; Arefi-Khonsari, F.

    2014-07-01

    A simple method to deposit photocatalytic TiO2 coatings, at a high rate (20-40 µm s-1), and with a high porosity, is reported in this paper. This method, which allows the treatment of membranes (with an 800 nm pore size), is based on the introduction of a liquid precursor sprayed into an open-air atmospheric pressure plasma jet (APPJ). The photocatalytic activity of the TiO2 thin films prepared by APPJ have been compared with our best N-doped TiO2 thin films, deposited by reactive radio frequency (RF) magnetron sputtering, previously reported in the literature. The morphology, chemical composition, photoelectrochemical, and photocatalytic properties of the coatings have been studied in this paper. Significant control of the porosity and crystallinity was achieved by varying the deposition parameters and the annealing temperature. Under optimized conditions, the TiO2 coatings deposited by APPJ are characterized by a higher photocatalytic activity as compared to the optimized thin films deposited by RF sputtering. This difference can be explained by the higher specific surface of the APPJ coatings. Finally, the most interesting characteristic of this APPJ-liquid spray process is its capacity to treat membranes without blocking the pores, and to produce photocatalytic membranes which can efficiently combine filtration and photocatalysis for water treatment.

  15. Vibrational and thermodynamic properties of Ar, N2, O2, H2 and CO adsorbed and condensed into (H,Na)-Y zeolite cages as studied by variable temperature IR spectroscopy.

    PubMed

    Gribov, Evgueni N; Cocina, Donato; Spoto, Giuseppe; Bordiga, Silvia; Ricchiardi, Gabriele; Zecchina, Adriano

    2006-03-14

    The adsorption of Ar, H2, O2, N2 and CO on (H,Na)-Y zeolite (Si/Al = 2.9, H+/Na+ approximately 5) has been studied at variable-temperature (90-20 K) and sub-atmospheric pressure (0-40 mbar) by FTIR spectroscopy. Unprecedented filling conditions of the zeolite cavities were attained, which allowed the investigation of very weakly adsorbed species and of condensed, liquid-like or solid-like, phases. Two pressure regimes were singled out, characterized by: (i) specific interaction at low pressure of the probe molecules (P) with the internal Brønsted and Lewis sites, and (ii) multilayer adsorption at higher pressure. In the case of CO the perturbation of the protonic sites located inside the sodalite cages was also observed. As the molecule is too large to penetrate the sodalite cage, the perturbation is thought to involve a proton jump tunneling mechanism. The adsorption energy for the (HF)OH...P (P = Ar, H2, O2, N2 and CO) specific interaction involving the high frequency Brønsted acid sites exposed in the supercages was derived following the VTIR (variable temperature infrared spectroscopy) method described by E. Garrone and C. Otero Areán (Chem. Soc. Rev., 2005, 34, 846).

  16. Synthesis, spectral and electrochemical studies of Cu(II) and Ni(II) complexes with new N 2O 2 ligands: A new precursor capable of depositing copper nanoparticles using thermal reduction

    NASA Astrophysics Data System (ADS)

    Habibi, Mohammad Hossein; Mokhtari, Reza; Mikhak, Maryam; Amirnasr, Mehdi; Amiri, Ahmad

    2011-09-01

    Cu(II) and Ni(II) complexes of the general type [M(N 2O 2)] are described. The N 2O 2 ligands used are [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine] (HOMeSalpn) and [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,2-diamine (HOMeSalpr). These complexes have been characterized by IR, UV-vis, CV, TG-DTA and 1H NMR spectroscopy. The electrochemical behavior of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to Cu(II)-Cu(I) and Ni(II)-Ni(I) is electrochemically irreversible. The new copper complexes have been applied for the preparation of copper nanoparticles using non-ionic surfactant (Triton X-100) by thermal reduction. The copper nanoparticles with average size of 48 nm were formed by thermal reduction of [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine]copper(II) in the presence of triphenylphosphine thus releasing the reduced copper and affording the high-purity copper nanoparticles.

  17. Synthesis, spectral and electrochemical studies of Cu(II) and Ni(II) complexes with new N2O2 ligands: a new precursor capable of depositing copper nanoparticles using thermal reduction.

    PubMed

    Habibi, Mohammad Hossein; Mokhtari, Reza; Mikhak, Maryam; Amirnasr, Mehdi; Amiri, Ahmad

    2011-09-01

    Cu(II) and Ni(II) complexes of the general type [M(N2O2)] are described. The N2O2 ligands used are [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine] (HOMeSalpn) and [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,2-diamine (HOMeSalpr). These complexes have been characterized by IR, UV-vis, CV, TG-DTA and 1H NMR spectroscopy. The electrochemical behavior of these complexes at a glassy carbon electrode in acetonitrile solution indicates that the first reduction process corresponding to Cu(II)-Cu(I) and Ni(II)-Ni(I) is electrochemically irreversible. The new copper complexes have been applied for the preparation of copper nanoparticles using non-ionic surfactant (Triton X-100) by thermal reduction. The copper nanoparticles with average size of 48nm were formed by thermal reduction of [N,N'-bis(2-hydroxy-6-methoxybenzylidene)propane-1,3-diamine]copper(II) in the presence of triphenylphosphine thus releasing the reduced copper and affording the high-purity copper nanoparticles.

  18. Long-term measurements of atmospheric trace gases (CO2, CH4, N2O, SF6, CO, H2), O2, and δ13CH4 isotopes at Weybourne Atmospheric Observatory, UK: past, present and future

    NASA Astrophysics Data System (ADS)

    Manning, Andrew C.; Forster, Grant L.; Oram, David E.; Reeves, Claire E.; Pickers, Penelope A.; Barningham, S. Thomas; Sturges, William T.; Bandy, Brian; Nisbet, Euan G.; Lowry, David; Fisher, Rebecca; Fleming, Zoe

    2016-04-01

    The Weybourne Atmospheric Observatory (WAO) is situated on the north Norfolk Coast (52.95°N, 1.13°E) in the United Kingdom and is run by the University of East Anglia (UEA), with support from the UK National Centre for Atmospheric Science (NCAS). In 2016, the WAO became a UK-ICOS (Integrated Carbon Observing System) monitoring station. Since 2008, we have been collecting high-precision long-term in situ measurements of atmospheric carbon dioxide (CO2), oxygen (O2), carbon monoxide (CO) and molecular hydrogen (H2), as well as regular bag sampling for δ13CH4. In early 2013, the measurement of atmospheric methane (CH4) commenced, and nitrous oxide (N2O) and sulphur hexafluoride (SF6) began in 2014. We summarise the CO2, O2, CH4, N2O, SF6, CO, H2 and δ13CH4 measurements made to date and highlight some key features observed (e.g. seasonal cycles, long-term trends, pollution events and deposition events). We summarise how the long-term measurements fit into other broader projects which have helped to support the long term time-series at WAO over the years, and highlight how we contribute to broader global atmospheric observation networks.

  19. Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

    PubMed Central

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-01-01

    Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm−2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm−2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms. PMID:25765731

  20. Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

    NASA Astrophysics Data System (ADS)

    Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

    2015-03-01

    Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm-2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm-2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.

  1. Surface diffusion control of the photocatalytic oxidation in air/TiO2 heterogeneous reactors

    NASA Astrophysics Data System (ADS)

    Tsekov, R.; Evstatieva, E.; Smirniotis, P. G.

    2002-10-01

    The diffusion of superoxide radical anions on the surface of TiO 2 catalysts is theoretically considered as an important step in the kinetics of photocatalytic oxidation of toxic pollutants. A detailed analysis is performed to discriminate the effects of rotation and adsorption bond vibrations on the diffusion coefficient. A resonant dependence of the diffusivity on the lattice parameters of the TiO 2 surface is discovered showing that the most rapid diffusion takes place when the lattice parameters are twice as large as the the bond length of the superoxide radical anions. Whereas the rotation and vibrations normal to the catalyst surface are important, the anion bond vibrations do not affect the diffusivity due to their low amplitudes as compared to the lattice parameters.

  2. Improved Wetting Characteristics in TiO2–Modified Ag-CuO Air Braze Filler Metals

    SciTech Connect

    Weil, K. Scott; Kim, Jin Yong; Hardy, John S.; Darsell, Jens T.

    2006-01-04

    A silver-based joining technique referred to as reactive air brazing (RAB) has been recently developed for joining high temperature structural ceramic components of the type used in high-temperature electrochemical devices. In prior work, it was found that additions of CuO to silver have a significant effect on the wettability and joint strength characteristics of the resulting braze on polycrystalline alumina substrates. More recently, it has been found that by adding as little as 0.5 mol % titania to these Ag-CuO brazes, the wettability of the RAB on alumina surfaces is further enhanced. The results of wettabilty measurements of Ag-CuO-TiO2 RAB compositions on alumina will be presented along with the microstructural characterization of Ag-CuO-TiO2 braze joints in alumina.

  3. Effect of metal in M3(btc)2 and M2(dobdc) MOFs for O2/N2 separations: A combined density functional theory and experimental study

    DOE PAGES

    Parkes, Marie V.; Sava Gallis, Dorina F.; Greathouse, Jeffery A.; ...

    2015-03-02

    Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air could lead to new sorbents for the oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate metal-organic frameworks has been undertaken. Dispersion-corrected density functional theory methods were used to calculate the oxygen and nitrogen binding energies with each of fourteen metals, respectively, substituted into two MOF series, M2(dobdc) and M3(btc)2. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trendmore » in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Altogether, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen, and that the MOF structural type is less important than the metal identity.« less

  4. Using elastin protein to develop highly efficient air cathodes for lithium-O2 batteries

    NASA Astrophysics Data System (ADS)

    Guo, Guilue; Yao, Xin; Ang, Huixiang; Tan, Huiteng; Zhang, Yu; Guo, Yuanyuan; Fong, Eileen; Yan, Qingyu

    2016-01-01

    Transition metal-nitrogen/carbon (M-N/C, M = Fe, Co) catalysts are synthesized using environmentally friendly histidine-tag-rich elastin protein beads, metal sulfate and water soluble carbon nanotubes followed by post-annealing and acid leaching processes. The obtained catalysts are used as cathode materials in lithium-O2 batteries. It has been discovered that during discharge, Li2O2 nanoparticles first nucleate and grow around the bead-decorated CNT regions (M-N/C centres) and coat on the catalysts at a high degree of discharge. The Fe-N/C catalyst-based cathodes deliver a capacity of 12 441 mAh g-1 at a current density of 100 mA g-1. When they were cycled at a limited capacity of 800 mAh g-1 at current densities of 200 or 400 mA g-1, these cathodes showed stable charge voltages of ˜3.65 or 3.90 V, corresponding to energy efficiencies of ˜71.2 or 65.1%, respectively. These results are considerably superior to those of the cathodes based on bare annealed CNTs, which prove that the Fe-N/C catalysts developed here are promising for use in non-aqueous lithium-O2 battery cathodes.

  5. Using elastin protein to develop highly efficient air cathodes for lithium-O2 batteries.

    PubMed

    Guo, Guilue; Yao, Xin; Ang, Huixiang; Tan, Huiteng; Zhang, Yu; Guo, Yuanyuan; Fong, Eileen; Yan, Qingyu

    2016-01-29

    Transition metal-nitrogen/carbon (M-N/C, M = Fe, Co) catalysts are synthesized using environmentally friendly histidine-tag-rich elastin protein beads, metal sulfate and water soluble carbon nanotubes followed by post-annealing and acid leaching processes. The obtained catalysts are used as cathode materials in lithium-O2 batteries. It has been discovered that during discharge, Li2O2 nanoparticles first nucleate and grow around the bead-decorated CNT regions (M-N/C centres) and coat on the catalysts at a high degree of discharge. The Fe-N/C catalyst-based cathodes deliver a capacity of 12,441 mAh g(-1) at a current density of 100 mA g(-1). When they were cycled at a limited capacity of 800 mAh g(-1) at current densities of 200 or 400 mA g(-1), these cathodes showed stable charge voltages of ∼3.65 or 3.90 V, corresponding to energy efficiencies of ∼71.2 or 65.1%, respectively. These results are considerably superior to those of the cathodes based on bare annealed CNTs, which prove that the Fe-N/C catalysts developed here are promising for use in non-aqueous lithium-O2 battery cathodes.

  6. Effects of variation in background mixing ratios of N2, O2, and Ar on the measurement of δ18O-H2O and δ2H-H2O values by cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, Jennifer E.; Rella, Chris W.

    2017-08-01

    Cavity ring-down spectrometers have generally been designed to operate under conditions in which the background gas has a constant composition. However, there are a number of observational and experimental situations of interest in which the background gas has a variable composition. In this study, we examine the effect of background gas composition on a cavity ring-down spectrometer that measures δ18O-H2O and δ2H-H2O values based on the amplitude of water isotopologue absorption features around 7184 cm-1 (L2120-i, Picarro, Inc.). For background mixtures balanced with N2, the apparent δ18O values deviate from true values by -0.50 ± 0.001 ‰ O2 %-1 and -0.57 ± 0.001 ‰ Ar %-1, and apparent δ2H values deviate from true values by 0.26 ± 0.004 ‰ O2 %-1 and 0.42 ± 0.004 ‰ Ar %-1. The artifacts are the result of broadening, narrowing, and shifting of both the target absorption lines and strong neighboring lines. While the background-induced isotopic artifacts can largely be corrected with simple empirical or semi-mechanistic models, neither type of model is capable of completely correcting the isotopic artifacts to within the inherent instrument precision. The development of strategies for dynamically detecting and accommodating background variation in N2, O2, and/or Ar would facilitate the application of cavity ring-down spectrometers to a new class of observations and experiments.

  7. Visible-Light Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

    NASA Technical Reports Server (NTRS)

    Coutts, Janelle L.; Hintze, Paul E.; Clausen, Christian A.; Richards, Jeffrey T.

    2014-01-01

    Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure.

  8. Degradation of phenol via wet-air oxidation over CuO/CeO2-ZrO2 nanocatalyst synthesized employing ultrasound energy: physicochemical characterization and catalytic performance.

    PubMed

    Parvas, Mohsen; Haghighi, Mohammad; Allahyari, Somaiyeh

    2014-01-01

    Catalytic wet air oxidation (CWAO) of phenol was carried out under atmospheric pressure of oxygen at 160 degrees C in a stirred batch reactor over copper catalysts supported by CeO2-ZrO2. The copper with different loadings were impregnated over the composite support by a sonication process. The catalysts were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray analysis (EDX), Brunauer-Emmett-Teller (BET) specific surface area and Fourier-transformed infrared analyses. Characteristic peaks attributed to copper were not found in XRD patterns even at high loadings, but based on EDX results, the existence of copper particles was confirmed. It means that sonochemical synthesis method even at high loadings produced small copper particles with low crystallinity and excellent dispersion over the CeO2-ZrO2 composite. FESEM micrographs indicated just slight enhancement in particle size at high loadings of Cu. Blank CWAO experiments illustrated low conversion of phenol using bare CeO2-ZrO2 support. Although some agglomeration of particles was found at high loadings of copper but owning to the fact that almost all ZrO2 particles incorporated into the CeO2 lattice at high contents of Cu, catalyst activity not only did not decrease but also the phenol conversion reached to the higher values. The optimal catalyst loading for phenol degradation was found to be 9 g/l. Complete conversion of phenol was achieved using CuO/CeO2-ZrO2 in 9 g/l catalyst loading with initial phenol concentration of 1000 ppm after 3 h of reaction.

  9. Tribology of Si/SiO2 in humid air: transition from severe chemical wear to wearless behavior at nanoscale.

    PubMed

    Chen, Lei; He, Hongtu; Wang, Xiaodong; Kim, Seong H; Qian, Linmao

    2015-01-13

    Wear at sliding interfaces of silicon is a main cause for material loss in nanomanufacturing and device failure in microelectromechanical system (MEMS) applications. However, a comprehensive understanding of the nanoscale wear mechanisms of silicon in ambient conditions is still lacking. Here, we report the chemical wear of single crystalline silicon, a material used for micro/nanoscale devices, in humid air under the contact pressure lower than the material hardness. A transmission electron microscopy (TEM) analysis of the wear track confirmed that the wear of silicon in humid conditions originates from surface reactions without significant subsurface damages such as plastic deformation or fracture. When rubbed with a SiO2 ball, the single crystalline silicon surface exhibited transitions from severe wear in intermediate humidity to nearly wearless states at two opposite extremes: (a) low humidity and high sliding speed conditions and (b) high humidity and low speed conditions. These transitions suggested that at the sliding interfaces of Si/SiO2 at least two different tribochemical reactions play important roles. One would be the formation of a strong "hydrogen bonding bridge" between hydroxyl groups of two sliding interfaces and the other the removal of hydroxyl groups from the SiO2 surface. The experimental data indicated that the dominance of each reaction varies with the ambient humidity and sliding speed.

  10. Mean Ages of Stratospheric Air Derived From in Situ Observations of CO2, CH4, and N2O

    NASA Technical Reports Server (NTRS)

    Andrews, A. E.; Boering, K. A.; Daube, B. C.; Wofsy, S. C.; Loewenstein, M.; Jost, H.; Podolske, J. R.; Webster, C. R.; Herman, R. L.; Scott, D. C.; Einaudi, Franco (Technical Monitor)

    2001-01-01

    Accurate mean ages for stratospheric air have been derived from a spatially and temporally comprehensive set of in situ observations of CO2, CH4, and N2O obtained from 1992 to 1998 from the NASA ER-2 aircraft and balloon flights. Errors associated with the tropospheric CO2 seasonal cycle and interannual variations in the CO2 growth rate are less than 0.5 year throughout the stratosphere and less than 0.3 year for air older than 2 years (N2O less than 275 ppbv), indicating that the age spectra are broad enough to attenuate these influences over the time period covered by these observations. The distribution of mean age with latitude and altitude provides detailed, quantitative information about the general circulation of the stratosphere. At 20 km, sharp meridional gradients in the mean age are observed across the subtropics. Between 20 and 30 km, the average difference in mean age between the tropics and midlatitudes is approximately 2 years, with slightly smaller differences at higher and lower altitudes. The mean age in the midlatitude middle stratosphere (approx. 25-32 km) is relatively constant with respect to altitude at 5 plus or minus 0.5 years. Comparison with earlier balloon observations of CO2 dating back to the 1970s indicates that the mean age of air in this region has remained within 11 year of its current value over the last 25 years. A climatology of mean age is derived from the observed compact relationship between mean age and N2O. These characteristics of the distribution of mean age in the stratosphere will serve as critically needed diagnostics for models of stratospheric transport.

  11. Energy Transfer Collisional Process Involving Heteromolecular Collisions Between Methyl Fluoride and N_2, Ar, He, CO_2, and Air

    NASA Astrophysics Data System (ADS)

    Phillips, Dane J.; Everitt, Henry O.

    2013-06-01

    Time resolved IR/THz double resonance (DR) spectroscopy has been performed with a Q-switched CO_2 laser and heterodyne THz detection. The rate constants associated with allowed rotational- and vibrational-state changing collisions of CH_3F with N_2, Ar, He, CO_2, and air are measured by monitoring the temporal evolution of the absorption strength for numerous rotational transitions as a function of pressure. Collision partner dependent energy transfer processes are studied and compared with homomolecular collisions. Energy transfer maps and associated collisional cross sections will be presented for each collision partner.

  12. Air versus He-O2 Recompression Treatment of Decompression Sickness in Guinea Pigs

    DTIC Science & Technology

    1988-01-01

    le traitement do la MDC chez los cobayes apr~s des plong~es A IPair. Lila RS, MacCallum ME, Pitkin RB. Tratamiento do recompresioa con aire vs. He-C...2 pars enfermeded por desconipresioa en conejillos do indiss. Undersea Biomed Res 1988; 15(4):283- 300-So *studio el tratamiento do roconapresion con...del tratamiento mejoro con profundidades mayores con airs, pewo no con He-C),. Es"o datos indica las difereacias potenciales en Is respuesta alan

  13. [Alveolar arterial O2 gradient in patients with cardiopulmonary pathology. Its study at rest with respiration of environmental air].

    PubMed

    Martínez Guerra, M L; Fernández Bonett, P; Lupi Herrera, E

    1979-01-01

    The arterial oxygen pressure (PAO2) and the arterial carbon dioxide pressure (PACO2) are the mirror of the whole stage in alveolar ventilation, because there is a numerical correlation between them, in the alveolar air equation. In our material no difference was found when the respiratory cocient is used to calculate the equation modifying the PACO2 value. On the other hand, the PaO depends on a great amount of variables, i.e., the rationship V/Q. Qs/Qt and the arteriovenous oxygen difference in volume percentage, which reflect the functional stage of the gaseous interchange; other variables depend essentially of technical factors as the methodology used in the obtention and management of the samples and the measurement of the PAO2 at the laboratory. Thus, the alveolo-arterial oxigen Difference delta (A-a)O2 is considered as a mirror of the fluctuations in gaseous interchange, only if the alveolar ventilation the cardiac output, the systemic arterial-vein oxygen difference and in minor importance the respiratory cocient (RP remain constant. The delta (A-a)O2 is not always correlated with other parameters far from the gaseous interchange at lung level in the critically ill patient, for this, it has not a pronostic mecaning by itself. Nevertheless, we believe that delta (A-a)O2 continues being a useful measurement to evaluate the gaseous interchange if at the same time all the factors which may have influence in it are analysed. We consider, for trying to be simple in the management of the acute respiratory failure at the bedside that the (A-a)O2 must not be linked to only one parameter of the respiratory function, i.e. the intrapulmonar veno-arterial shunt, without considering the cardiac output and the systemic arterial-vein oxygen difference.

  14. Differential scattering cross sections for collisions of 0.5-, 1.5-, and 5.0-keV helium atoms with He, H2, N2, and O2. [for atmospheric processes modeling

    NASA Technical Reports Server (NTRS)

    Newman, J. H.; Smith, K. A.; Stebbings, R. F.; Chen, Y. S.

    1985-01-01

    This paper reports the first results of an experimental program established to provide cross section data for use in modeling various atmospheric processes. Absolute cross sections, differential in the scattering angle, have been measured for collisions of 0.5-, 1.5-, and 5.0-keV helium atoms with He, H2, N2, and O2 at laboratory scattering angles between 0.1 deg and 5 deg. The results are the sums of cross sections for elastic and inelastic scattering of helium atoms; charged collision products are not detected. Integration of the differential cross section data yields integral cross sections consistent with measurements by other workers. The apparatus employs a position-sensitive detector for both primary and scattered particles and uses a short target cell with a large exit aperture to ensure a simple and well-defined apparatus geometry.

  15. Impulsive rotational Raman scattering of N2 by a remote "air laser" in femtosecond laser filament.

    PubMed

    Ni, Jielei; Chu, Wei; Zhang, Haisu; Zeng, Bin; Yao, Jinping; Qiao, Lingling; Li, Guihua; Jing, Chenrui; Xie, Hongqiang; Xu, Huailiang; Cheng, Ya; Xu, Zhizhan

    2014-04-15

    We report on experimental realization of impulsive rotational Raman scattering from neutral nitrogen molecules in a femtosecond laser filament using an intense self-induced white-light seeding "air laser" generated during the filamentation of an 800 nm Ti:sapphire laser in nitrogen gas. The impulsive rotational Raman fingerprint signals are observed with a maximum conversion efficiency of ∼0.8%. Our observation provides a promising way of remote identification and location of chemical species in the atmosphere by a rotational Raman scattering of molecules.

  16. Co3O4-CeO2/C as a Highly Active Electrocatalyst for Oxygen Reduction Reaction in Al-Air Batteries.

    PubMed

    Liu, Kun; Huang, Xiaobing; Wang, Haiyan; Li, Fuzhi; Tang, Yougen; Li, Jingsha; Shao, Minhua

    2016-12-21

    Developing high-performance and low-cost electrocatalysts for oxygen reduction reaction (ORR) is still a great challenge for Al-air batteries. Herein, CeO2, a unique ORR promoter, was incorporated into ketjenblack (KB) supported Co3O4 catalyst. We developed a facile two-step hydrothermal approach to fabricate Co3O4-CeO2/KB as a high-performance ORR catalyst for Al-air batteries. The ORR activity of Co3O4/KB was significantly increased by mixing with CeO2 nanoparticles. In addition, the Co3O4-CeO2/KB showed a better electrocatalytic performance and stability than 20 wt % Pt/C in alkaline electrolytes, making it a good candidate for highly active ORR catalysts. Co3O4-CeO2/KB favored a four-electron pathway in ORR due to the synergistic interactions between CeO2 and Co3O4. In full cell tests, the Co3O4-CeO2/KB exhibited a higher discharge voltage plateau than CeO2/KB and Co3O4/KB when used in cathode in Al-air batteries.

  17. Atomic layer deposition of amorphous oxygen-deficient TiO2-x on carbon nanotubes as cathode materials for lithium-air batteries

    NASA Astrophysics Data System (ADS)

    Yang, Jingbo; Ma, Dingtao; Li, Yongliang; Zhang, Peixin; Mi, Hongwei; Deng, Libo; Sun, Lingna; Ren, Xiangzhong

    2017-08-01

    The amorphous oxygen-deficient TiO2-x thin layer coated carbon nanotubes (CNTs) are synthesized by atomic layer deposition and employed as cathode materials for lithium-air battery. The cathode demonstrates high electrocatalytic activity toward electrode reactions, resulting from the introduction of oxygen-deficient TiO2-x into the nanocomposites. It is found that the intrinsically isotropic nature of amorphous TiO2 which a certain amount of Ti3.5+ and Ti3+ can improve the catalytic activity. Consequently, the battery with the corresponded CNT@TiO2-x cathode shows high discharge/charge capacities and good cycling performance, which the cyclic retention of more than 90 cycles are achieved, while with the pristine CNTs only 50 cycles are obtained. This study provides an approach to fabricate cathode materials for lithium-air battery and moreover clarifies the influence of oxygen vacancies of TiO2 on the electrochemical performance.

  18. Air stability of TiO2/PbS colloidal nanoparticle solar cells and its impact on power efficiency

    NASA Astrophysics Data System (ADS)

    Zhai, Guangmei; Bezryadina, Anna; Breeze, Alison J.; Zhang, Daoli; Alers, Glenn B.; Carter, Sue A.

    2011-08-01

    The short-term (less than 1 hour) exposure of TiO2/PbS quantum dot photovoltaics to air increases the open circuit voltage (Voc) and fill factor (FF) while slightly decreasing the short circuit current density (Jsc), leading to a power conversion efficiency above 4% and a peak external quantum efficiency over 80% for 1.1 eV PbS. The resulting Jsc, Voc, and FF under 100 mW/cm2 AM1.5 are 18.6 mA/cm2, 0.517 V, and 42% for 1.1 eV PbS and 8.03 mA/cm2, 0.655 V, and 35% for 1.7 eV PbS, respectively. Long-term air exposures result in much lower conductivities. Furthermore, short-term air exposure effects are fully reversible upon removal from air, and longer-term effects are mostly reversible through soaking in 1,2-ethanedithiol.

  19. Theoretical studies of UO2(H2O)n2+,NpO2(H2O)n+, and PuO2(H2O)n2+ complexes (n=4-6) in aqueous solution and gas phase

    NASA Astrophysics Data System (ADS)

    Cao, Zhiji; Balasubramanian, K.

    2005-09-01

    Extensive ab initio calculations both in gas phase and solution have been carried out to study the equilibrium structure, vibrational frequencies, and bonding characteristics of various actinyl (UO22+,NpO2+, and PuO22+) and their hydrated forms, AnO2(H2O)nz + (n =4, 5, and 6). Bulk solvent effects were studied using a continuum method. The geometries were fully optimized at the coupled-cluster singles + doubles (CCSD), density-functional theory (DFT), and Møller-Plesset (MP2) level of theories. In addition vibrational frequencies have been obtained at the CCSD as well as MP2/DFT levels. The results show that both the short-range and long-range solvent effects are important. The combined discrete-continuum model, in which the ionic solute and the solvent molecules in the first and second solvation shells are treated quantum mechanically while the solvent is simulated by a continuum model, can predict accurately the bonding characteristics. Moreover, our values of solvation free energies suggest that five- and six-coordinations are equally preferred for UO22+, and five-coordinated species are preferred for NpO2+ and PuO22+. On the basis of combined quantum-chemical and continuum treatments of the hydrated complexes, we are able to determine the optimal cavity radii for the solvation models. The coupled-cluster computations with large basis sets were employed for the vibrational spectra and equilibrium geometries both of which compare quite favorably with experiment. Our most accurate computations reveal that both five- and six-coordination complexes are important for these species.

  20. Markers of lipid oxidative damage among office workers exposed intermittently to air pollutants including nanoTiO2 particles.

    PubMed

    Pelclova, Daniela; Zdimal, Vladimir; Kacer, Petr; Komarc, Martin; Fenclova, Zdenka; Vlckova, Stepanka; Zikova, Nadezda; Schwarz, Jaroslav; Makes, Otakar; Navratil, Tomas; Zakharov, Sergey; Bello, Dhimiter

    2017-03-01

    Nanoscale titanium dioxide (nanoTiO2) is a commercially important nanomaterial used in numerous applications. Experimental studies with nanotitania have documented lung injury and inflammation, oxidative stress, and genotoxicity. Production workers in TiO2 manufacturing with a high proportion of nanoparticles and a mixture of other air pollutants, such as gases and organic aerosols, had increased markers of oxidative stress, including DNA and protein damage, as well as lipid peroxidation in their exhaled breath condensate (EBC) compared to unexposed controls. Office workers were observed to get intermittent exposures to nanoTiO2 during their process monitoring. The aim of this study was to investigate the impact of such short-term exposures on the markers of health effects in office workers relative to production workers from the same factory. Twenty-two office employees were examined. They were occupationally exposed to (nano)TiO2 aerosol during their daily visits of the production area for an average of 14±9 min/day. Median particle number concentration in office workers while in the production area was 2.32×104/cm3. About 80% of the particles were <100 nm in diameter. A panel of biomarkers of lipid oxidation, specifically malondialdehyde (MDA), 4-hydroxy-trans-hexenal (HHE), 4-hydroxy-trans-nonenal (HNE), 8-isoprostaglandin F2α (8-isoprostane), and aldehydes C6-C12, were studied in the EBC and urine of office workers and 14 unexposed controls. Nine markers of lipid oxidation were elevated in the EBC of office employees relative to controls (p<0.05); only 8-isoprostane and C11 were not increased. Significant association was found in the multivariate analysis between their employment in the TiO2 production plant and EBC markers of lipid oxidation. No association was seen with age, lifestyle factors, or environmental air contamination. The EBC markers in office employees reached about 50% of the levels measured in production workers, and the difference between

  1. Statistical temperature profile retrievals in clear-air using passive 118-GHz O2 observations

    NASA Technical Reports Server (NTRS)

    Gasiewski, A. J.; Johnson, J. T.

    1993-01-01

    The clean-air temperature profile accuracy yielded by a localized linear statistical retrieval operator applied to passive aircraft-based 118-GHz spectra is demonstrated. A comparison of the statistically and physically derived correlation coefficients of antenna temperature and kinetic temperature furnishes a physical justification of the statistical retrieval technique. The atmospheric temperature mean and covariance significantly depend on such geophysical parameters as latitude, longitude, local season, and time, as well as the prevailing meteorological state and orographic effects.

  2. Statistical temperature profile retrievals in clear-air using passive 118-GHz O2 observations

    NASA Technical Reports Server (NTRS)

    Gasiewski, A. J.; Johnson, J. T.

    1993-01-01

    The clean-air temperature profile accuracy yielded by a localized linear statistical retrieval operator applied to passive aircraft-based 118-GHz spectra is demonstrated. A comparison of the statistically and physically derived correlation coefficients of antenna temperature and kinetic temperature furnishes a physical justification of the statistical retrieval technique. The atmospheric temperature mean and covariance significantly depend on such geophysical parameters as latitude, longitude, local season, and time, as well as the prevailing meteorological state and orographic effects.

  3. Effects of He-O2 Breathing during Experimental Decompression Sickness Following Air Dives

    DTIC Science & Technology

    1987-03-01

    ventilator volume or rate was made during the experiment. The oxygen content of the He-0 2 mixture used in the He-Or group was measured using a...e ne modifia pas ces rdponses. mats la respiratton de He-O? produtst une augmentation de 11% dans Ia rdsistance vasculaire pulmonaire (RVP). Chez 3...d’une plong~e A F’air peut aggraver l’obstruction vasculaire pulmonaire. plongde hdlium-oxygtne maladie de decompression suffocation embolie gazeuse

  4. Co3O4 nanoparticle-modified MnO2 nanotube bifunctional oxygen cathode catalysts for rechargeable zinc-air batteries

    NASA Astrophysics Data System (ADS)

    Du, Guojun; Liu, Xiaogang; Zong, Yun; Hor, T. S. Andy; Yu, Aishui; Liu, Zhaolin

    2013-05-01

    We report the preparation of MnO2 nanotubes functionalized with Co3O4 nanoparticles and their use as bifunctional air cathode catalysts for oxygen reduction reaction and oxygen evolution reaction in rechargeable zinc-air batteries. These hybrid MnO2/Co3O4 nanomaterials exhibit enhanced catalytic reactivity toward oxygen evolution reaction under alkaline conditions compared with that in the presence of MnO2 nanotubes or Co3O4 nanoparticles alone.We report the preparation of MnO2 nanotubes functionalized with Co3O4 nanoparticles and their use as bifunctional air cathode catalysts for oxygen reduction reaction and oxygen evolution reaction in rechargeable zinc-air batteries. These hybrid MnO2/Co3O4 nanomaterials exhibit enhanced catalytic reactivity toward oxygen evolution reaction under alkaline conditions compared with that in the presence of MnO2 nanotubes or Co3O4 nanoparticles alone. Electronic supplementary information (ESI) available: Zinc-air cell device, XPS survey scan and power density of the cell. See DOI: 10.1039/c3nr00300k

  5. Zn/gelled 6 M KOH/O 2 zinc-air battery

    NASA Astrophysics Data System (ADS)

    Mohamad, A. A.

    The gel electrolyte for the zinc-air cell was prepared by mixing hydroponics gel with a 6 M potassium hydroxide aqueous solution. The self-discharge of cells was characterized by measuring the open-circuit voltage. The effect of a discharge rate of 50 mA constant current on cell voltage and plateau hour, as well as the voltage-current and current density-power density were measured and analysed. The electrode degradation after discharge cycling was characterized by structural and surface methods. The oxidation of the electrode surface further blocked the utilization of the Zn anode and was identified as a cause for the failure of the cell.

  6. Temperature measurements in hypersonic air flows using laser-induced O2 fluorescence

    NASA Technical Reports Server (NTRS)

    Laufer, Gabriel; Mckenzie, Robert L.

    1988-01-01

    An investigation is reported of the use of laser-induced fluorescence on oxygen for the measurement of air temperature and its fluctuations owing to turbulence in hypersonic wind tunnel flows. The results show that for temperatures higher than 60 K and densities higher than 0.01 amagat, the uncertainty in the temperature measurement can be less than 2 percent if it is limited by photon-statistical noise. The measurement is unaffected by collisional quenching and, if the laser fluence is kept below 1.5 J/sq cm, it is also unaffected by nonlinear effects which are associated with depletion of the absorbing states.

  7. Temperature measurements in hypersonic air flows using laser-induced O2 fluorescence

    NASA Technical Reports Server (NTRS)

    Laufer, Gabriel; Mckenzie, Robert L.

    1988-01-01

    An investigation is reported of the use of laser-induced fluorescence on oxygen for the measurement of air temperature and its fluctuations owing to turbulence in hypersonic wind tunnel flows. The results show that for temperatures higher than 60 K and densities higher than 0.01 amagat, the uncertainty in the temperature measurement can be less than 2 percent if it is limited by photon-statistical noise. The measurement is unaffected by collisional quenching and, if the laser fluence is kept below 1.5 J/sq cm, it is also unaffected by nonlinear effects which are associated with depletion of the absorbing states.

  8. Formation of oxygen vacancies and Ti3+ state in TiO2 thin film and enhanced optical properties by air plasma treatment

    PubMed Central

    Bharti, Bandna; Kumar, Santosh; Lee, Heung-No; Kumar, Rajesh

    2016-01-01

    This is the first time we report that simply air plasma treatment can also enhances the optical absorbance and absorption region of titanium oxide (TiO2) films, while keeping them transparent. TiO2 thin films having moderate doping of Fe and Co exhibit significant enhancement in the aforementioned optical properties upon air plasma treatment. The moderate doping could facilitate the formation of charge trap centers or avoid the formation of charge recombination centers. Variation in surface species viz. Ti3+, Ti4+, O2−, oxygen vacancies, OH group and optical properties was studied using X-ray photon spectroscopy (XPS) and UV-Vis spectroscopy. The air plasma treatment caused enhanced optical absorbance and optical absorption region as revealed by the formation of Ti3+ and oxygen vacancies in the band gap of TiO2 films. The samples were treated in plasma with varying treatment time from 0 to 60 seconds. With the increasing treatment time, Ti3+ and oxygen vacancies increased in the Fe and Co doped TiO2 films leading to increased absorbance; however, the increase in optical absorption region/red shift (from 3.22 to 3.00 eV) was observed in Fe doped TiO2 films, on the contrary Co doped TiO2 films exhibited blue shift (from 3.36 to 3.62 eV) due to Burstein Moss shift. PMID:27572095

  9. RuO2 nanoparticles decorated MnOOH/C as effective bifunctional electrocatalysts for lithium-air battery cathodes with long-cycling stability

    NASA Astrophysics Data System (ADS)

    Kim, Gil-Pyo; Lim, Dongwook; Park, Inyeong; Park, Hyelee; Shim, Sang Eun; Baeck, Sung-Hyeon

    2016-08-01

    Manganite (MnOOH) is one of the most effective electrocatalysts for oxygen reduction reaction (ORR), and RuO2 nanoparticles exhibit high activity for oxygen evolution reaction (OER). We herein report a facile means of producing well dispersed RuO2/MnOOH on Ketjen black (RuO2/MnOOH/C) as a bifunctional catalyst for lithium-air (Li-air) batteries. RuO2/MnOOH/C was simply synthesized using a hydrothermal/precipitation based method, and was used as a cathode for a Li-air battery using a Swagelok-type cell. The importance of dispersing active catalysts on a carbon support was clearly demonstrated by textural, charge-discharge voltammetric, and electrochemical impedance spectroscopic (EIS) analyses, comparing results with a catalyst produced by physically mixing RuO2/MnOOH with carbon (RuO2/MnOOH + C). RuO2/MnOOH/C showed low overpotential and stable cycleability up to 170th cycles with 1000 mAh g-1 of charge-discharge capacity, which was attributed to its enhanced active surface area and low charge-transfer resistance. The results obtained suggest that this strategy can be widely applied to bifunctional electrocatalysis, such as secondary batteries and regenerative fuel cell (RFC).

  10. Formation of oxygen vacancies and Ti(3+) state in TiO2 thin film and enhanced optical properties by air plasma treatment.

    PubMed

    Bharti, Bandna; Kumar, Santosh; Lee, Heung-No; Kumar, Rajesh

    2016-08-30

    This is the first time we report that simply air plasma treatment can also enhances the optical absorbance and absorption region of titanium oxide (TiO2) films, while keeping them transparent. TiO2 thin films having moderate doping of Fe and Co exhibit significant enhancement in the aforementioned optical properties upon air plasma treatment. The moderate doping could facilitate the formation of charge trap centers or avoid the formation of charge recombination centers. Variation in surface species viz. Ti(3+), Ti(4+), O(2-), oxygen vacancies, OH group and optical properties was studied using X-ray photon spectroscopy (XPS) and UV-Vis spectroscopy. The air plasma treatment caused enhanced optical absorbance and optical absorption region as revealed by the formation of Ti(3+) and oxygen vacancies in the band gap of TiO2 films. The samples were treated in plasma with varying treatment time from 0 to 60 seconds. With the increasing treatment time, Ti(3+) and oxygen vacancies increased in the Fe and Co doped TiO2 films leading to increased absorbance; however, the increase in optical absorption region/red shift (from 3.22 to 3.00 eV) was observed in Fe doped TiO2 films, on the contrary Co doped TiO2 films exhibited blue shift (from 3.36 to 3.62 eV) due to Burstein Moss shift.

  11. Formation of oxygen vacancies and Ti3+ state in TiO2 thin film and enhanced optical properties by air plasma treatment

    NASA Astrophysics Data System (ADS)

    Bharti, Bandna; Kumar, Santosh; Lee, Heung-No; Kumar, Rajesh

    2016-08-01

    This is the first time we report that simply air plasma treatment can also enhances the optical absorbance and absorption region of titanium oxide (TiO2) films, while keeping them transparent. TiO2 thin films having moderate doping of Fe and Co exhibit significant enhancement in the aforementioned optical properties upon air plasma treatment. The moderate doping could facilitate the formation of charge trap centers or avoid the formation of charge recombination centers. Variation in surface species viz. Ti3+, Ti4+, O2‑, oxygen vacancies, OH group and optical properties was studied using X-ray photon spectroscopy (XPS) and UV-Vis spectroscopy. The air plasma treatment caused enhanced optical absorbance and optical absorption region as revealed by the formation of Ti3+ and oxygen vacancies in the band gap of TiO2 films. The samples were treated in plasma with varying treatment time from 0 to 60 seconds. With the increasing treatment time, Ti3+ and oxygen vacancies increased in the Fe and Co doped TiO2 films leading to increased absorbance; however, the increase in optical absorption region/red shift (from 3.22 to 3.00 eV) was observed in Fe doped TiO2 films, on the contrary Co doped TiO2 films exhibited blue shift (from 3.36 to 3.62 eV) due to Burstein Moss shift.

  12. N2O molecular tagging velocimetry

    NASA Astrophysics Data System (ADS)

    ElBaz, A. M.; Pitz, R. W.

    2012-03-01

    A new seeded velocity measurement technique, N2O molecular tagging velocimetry (MTV), is developed to measure velocity in wind tunnels by photochemically creating an NO tag line. Nitrous oxide "laughing gas" is seeded into the air flow. A 193 nm ArF excimer laser dissociates the N2O to O(1D) that subsequently reacts with N2O to form NO. O2 fluorescence induced by the ArF laser "writes" the original position of the NO line. After a time delay, the shifted NO line is "read" by a 226-nm laser sheet and the velocity is determined by time-of-flight. At standard atmospheric conditions with 4% N2O in air, ˜1000 ppm of NO is photochemically created in an air jet based on experiment and simulation. Chemical kinetic simulations predict 800-1200 ppm of NO for 190-750 K at 1 atm and 850-1000 ppm of NO for 0.25-1 atm at 190 K. Decreasing the gas pressure (or increasing the temperature) increases the NO ppm level. The presence of humid air has no significant effect on NO formation. The very short NO formation time (<10 ns) makes the N2O MTV method amenable to low- and high-speed air flow measurements. The N2O MTV technique is demonstrated in air jet to measure its velocity profile. The N2O MTV method should work in other gas flows as well (e.g., helium) since the NO tag line is created by chemical reaction of N2O with O(1D) from N2O photodissociation and thus does not depend on the bulk gas composition.

  13. Colour changes of a historical Gotland sandstone caused by laser surface cleaning in ambient air and N2 flow

    NASA Astrophysics Data System (ADS)

    Jasińska, M.; Nowak, A.; Łukaszewicz, J. W.; Śliwiński, G.

    2008-07-01

    The surface discoloration due to laser cleaning was investigated for a historical Gotland sandstone. The difference in discoloration for cleaning performed in air and in the shielding environment of N2 flowing at low velocities was studied by means of colorimetry and scanning electron microscopy and energy dispersive X-ray spectroscopy techniques. For ablative removal of the natural as well as artificially applied encrustation a pulsed 1064-nm laser operated at a fluence of 0.5 J/cm2 was applied. It was observed that the natural colour variations (ΔL*=21; Δb*=23) of the stone can completely screen the laser-induced changes. Under conditions of shielding with nitrogen, darkening and yellowing slightly stronger than those occurring in the ambient air were revealed for the laser-cleaned, artificially crusted samples and the effect was independent of the gas-flow velocity. The observed difference confirmed the contribution of iron oxidation to the laser-induced yellowing and showed that the presence of oxygen in the ambient air affects favourably the cleaning by supporting removal of a variety of combustible surface remnants and crust components of organic as well as inorganic origin.

  14. Transcutaneous CO2/O2 and CO2/air suction in patients undergoing cataract surgery with retrobulbar anaesthesia.

    PubMed

    Schlager, A; Lorenz, I H; Luger, T J

    1998-12-01

    We investigated transcutaneous partial CO2 and O2 pressures and respiratory rate in unpremedicated elderly patients of ASA physical status 1 to 3 who underwent cataract surgery under retrobulbar anaesthesia. In group A no air suction was used. In group B suction was applied under the sterile drapes to avoid rebreathing of CO2. In group A transcutaneous partial CO2 pressure and respiratory rate significantly increased compared with baseline, whereas in group B they remained constant. In both groups transcutaneous partial O2 pressure and oxygen saturation as measured by pulse oximetry significantly rose after insufflating oxygen 31.min-1. Heart rate and mean arterial blood pressure remained constant. Our results demonstrate that the application of suction near the patient's head prevents CO2 rebreathing and subsequent hypercapnia associated with an elevated respiratory rate. The use of suction makes it unnecessary to raise oxygen administration. Suction combined with monitoring of partial CO2 pressure using transcutaneous sensors should be used in all ophthalmological operations under retrobulbar anaesthesia.

  15. Continuous Distributions of Ventilation-Perfusion Ratios in Normal Subjects Breathing Air and 100% O2

    PubMed Central

    Wagner, Peter D.; Laravuso, Raymond B.; Uhi, Richard R.; West, John B.

    1974-01-01

    A new method has been developed for measuring virtually continuous distributions of ventilation-perfusion ratios (V̇A/Q̇) based on the steadystate elimination of six gases of different solubilities. The method is applied here to 12 normal subjects, aged 21—60. In nine, the distributions were compared breathing air and 100% oxygen, while in the remaining three, effects of changes in posture were examined. In four young semirecumbent subjects (ages 21—24) the distributions of blood flow and ventilation with respect to V̇A/Q̇ were virtually log-normal with little dispersion (mean log standard deviations 0.43 and 0.35, respectively). The 95.5% range of both blood flow and ventilation was from V̇A/Q̇ ratios of 0.3—2.1, and there was no intrapulmonary shunt (V̇A/Q̇ of 0). On breathing oxygen, a shunt developed in three of these subjects, the mean value being 0.5% of the cardiac output. The five older subjects (ages 39—60) had broader distributions (mean log standard deviations, 0.76 and 0.44) containing areas with V̇A/Q ratios in the range 0.01—0.1 in three subjects. As for the young subjects, there was no shunt breathing air, but all five developed a shunt breathing oxygen (mean value 3.2%), and in one the value was 10.7%. Postural changes were generally those expected from the known effects of gravity, with more ventilation to high VA/Q areas when the subjects were erect than supine. Measurements of the shunt while breathing oxygen, the Bohr CO2 dead space, and the alveolar-arterial oxygen difference were all consistent with the observed distributions. Since the method involves only a short infusion of dissolved inert gases, sampling of arterial blood and expired gas, and measurement of cardiac output and minute ventilation, we conclude that it is well suited to the investigation of pulmonary gas exchange in man. PMID:4601004

  16. Impact of air-exposure on the chemical and electronic structure ofZnO:Zn3N2 thin films

    SciTech Connect

    Bar, M.; Ahn, K.-S.; Shet, S.; Yan, Y.; Weinhardt, L.; Fuchs, O.; Blum, M.; Pookpanratana, S.; George, K.; Yang, W.; Denlinger, J.D.; Al-Jassim, M.; Heske, C.

    2008-09-08

    The chemical and electronic surface structure of ZnO:Zn3N2 ("ZnO:N") thin films with different N contents was investigated by soft x-ray emission spectroscopy. Upon exposure to ambient air (in contrast to storage in vacuum), the chemical and electronic surface structure of the ZnO:N films changes substantially. In particular, we find that the Zn3N2/(Zn3N2+ZnO) ratio decreases with exposure time and that this change depends on the initial N content. We suggest a degradation mechanism based on the reaction of the Zn3N2 content with atmospheric humidity.

  17. Thermal decomposition of sewage sludge under N2, CO2 and air: Gas characterization and kinetic analysis.

    PubMed

    Hernández, Ana Belén; Okonta, Felix; Freeman, Ntuli

    2017-07-01

    Thermochemical valorisation processes that allow energy to be recovered from sewage sludge, such as pyrolysis and gasification, have demonstrated great potential as convenient alternatives to conventional sewage sludge disposal technologies. Moreover, these processes may benefit from CO2 recycling. Today, the scaling up of these technologies requires an advanced knowledge of the reactivity of sewage sludge and the characteristics of the products, specific to the thermochemical process. In this study the behaviour of sewage sludge during thermochemical conversion, under different atmospheres (N2, CO2 and air), was studied, using TGA-FTIR, in order to understand the effects of different atmospheric gases on the kinetics of degradation and on the gaseous products. The different steps observed during the solid degradation were related with the production of different gaseous compounds. A higher oxidative degree of the atmosphere surrounding the sample resulted in higher reaction rates and a shift of the degradation mechanisms to lower temperatures, especially for the mechanisms taking place at temperatures above 400 °C. Finally, a multiple first-order reaction model was proposed to compare the kinetic parameters obtained under different atmospheres. Overall, the highest activation energies were obtained for combustion. This work proves that CO2, an intermediate oxidative atmosphere between N2 and air, results in an intermediate behaviour (intermediate peaks in the derivative thermogravimetric curves and intermediate activation energies) during the thermochemical decomposition of sewage sludge. Overall, it can be concluded that the kinetics of these different processes require a different approach for their scaling up and specific consideration of their characteristic reaction temperatures and rates should be evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. The use of radiative transition rates to study the changes in the excitation of Cu ions in a Ne glow discharge caused by small additions of H2, O2 and N2

    NASA Astrophysics Data System (ADS)

    Weiss, Z.; Steers, E. B. M.; Mushtaq, S.; Hoffmann, V.; Pickering, J. C.

    2016-04-01

    The excitation of Cu+ ions in a Ne glow discharge with small additions of H2, O2 and N2 was studied. Ratios of radiative transition rates between different Cu II levels in a discharge in neon, with and without the molecular gas added, were calculated, and the formalism of transition rate ratio (TRR) diagrams was developed and used to study the changing excitation conditions. Virtually no changes in the excitation of Cu+ ions occur in a neon discharge if nitrogen is added. Additions of hydrogen and oxygen to neon as the discharge gas affect excitation of the 4d, 5s and some other Cu II levels in the vicinity of the ionization energy of neon (21.56 eV). Also some lower Cu II levels, excited by radiative decay of those higher energy levels, are affected. The 4p 3P2 level at 15.96 eV is enhanced by additions of hydrogen. It was suggested that this enhancement is caused by the asymmetric charge transfer reaction between neutral copper atoms and the H2+ molecular ions.

  19. Synthesis, structure and physicochemical characterization of the hybrid material [C6H16N2O]2 SnCl6·2Cl·2H2O

    NASA Astrophysics Data System (ADS)

    Belhaj Salah, S.; Pereira da Silva, P. S.; Lefebvre, F.; Ben Nasr, C.; Ammar, S.; Mrad, M. L.

    2017-04-01

    The current study reports the chemical preparation, crystal structure, Hirshfeld surface analysis and spectroscopic characterization of the novel compound [C6H16N2O]2SnCl6·2Cl·2H2O. This compound crystallizes in the triclinic system (space group P - 1, Z = 1) with the following unit cell dimensions: a = 7.9764(9), b = 8.2703(9), c = 12.1103(14)Å, α = 84.469(6), β = 75.679(6), and γ = 64.066(5)°. The structure was solved using 3093 independent reflections down to R = 0.020. The atomic arrangement shows alternation of organic and inorganic entities. The cohesion between these entities is ensured by Nsbnd H…Cl and Osbnd H…Cl hydrogen bonds that build a three-dimensional network. The 3D Hirshfeld surfaces and the associated 2D fingerprint plots were investigated for intermolecular interactions. The 13C and 15N CP-MAS NMR spectra are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the IR and NMR bands. X-ray powder, XPS and UV spectrum have been carried out. The DSC profile shows that the title material exhibits dehydration at 339 K.

  20. Satellite retrieval of cloud properties from the O2 A-band for air quality and climate applications

    NASA Astrophysics Data System (ADS)

    Wang, P.; Stammes, P.; van der A, R.

    2009-04-01

    The FRESCO (Fast Retrieval Scheme for Clouds from the Oxygen A-band) algorithm has been used to retrieve cloud information from measurements of the O2 A-band around 760 nm by GOME, SCIAMACHY and GOME-2. The cloud parameters retrieved by FRESCO are the effective cloud fraction and cloud pressure, which are used for cloud correction in the retrieval of trace gases like O3 and NO2. To improve the cloud pressure retrieval for partly cloudy scenes, single Rayleigh scattering has been included in an improved version of the algorithm, called FRESCO+. FRESCO+ gives more reliable cloud pressures over partly cloudy pixels. Simulations and comparisons with ground-based radar measurements of clouds shows that the FRESCO+ cloud pressure is about the optical midlevel of the cloud. Globally averaged, the FRESCO+ cloud pressure is about 50 hPa higher than the FRESCO cloud pressure, while the FRESCO+ effective cloud fraction is about 0.01 larger. From ground-based validation (P. Wang et al., Atmos. Chem. Phys., 8, 6565-6576, 2008) it appears that the FRESCO+ cloud retrievals improve the retrieval of tropospheric NO2 as compared to FRESCO. So FRESCO+ contributes to better monitoring of air quality from space. The FRESCO+ cloud algorithm has been applied to GOME and SCIAMACHY measurements since the beginning of the missions. Monthly averaged SCIAMACHY FRESCO+ effective cloud fraction and cloud pressure maps show similar patterns as the ISCCP cloud maps, although there are some differences, due to the different meaning of the cloud products and due to the fact that photons in the O2 A-band penetrate into clouds. The 6-year averaged seasonal cloud maps from SCIAMACHY data have good agreement with the global circulation patterns. Therefore, the FRESCO+ products are not only efficient for cloud correction of trace gas retrievals but also contribute additional information for climate research.

  1. Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

    NASA Technical Reports Server (NTRS)

    Coutts, Janelle L.; Hintze, Paul E.; Clausen, Christian; Richards, Jeffrey Todd

    2014-01-01

    Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of

  2. Elevated α-methyl-γ-hydroxy-1,N2-propano-2'-deoxyguanosine levels in urinary samples from individuals exposed to urban air pollution.

    PubMed

    Garcia, Camila C M; Freitas, Florêncio P; Sanchez, Angélica B; Di Mascio, Paolo; Medeiros, Marisa H G

    2013-11-18

    Acetaldehyde and crotonaldehyde are genotoxic aldehydes present in tobacco smoke and vehicle exhaust. The reaction of these aldehydes with 2'-deoxyguanosine in DNA produces α-methyl-γ-hydroxy-1,N(2)-propano-2'-deoxyguanosine (1,N(2)-propanodGuo). Online HPLC-tandem mass spectrometry was utilized to accurately quantify 1,N(2)-propanodGuo in human urinary samples from 47 residents of São Paulo City (SP) and 35 residents of the rural municipality of São João da Boa Vista (SJBV) in the state of São Paulo. Significantly higher 1,N(2)-propanodGuo levels were found in the samples from SP donors than in samples from SJBV donors. Our results provide the first evidence that elevated levels of 1,N(2)-propanodGuo in urinary samples may be correlated with urban air pollution.

  3. Computed self-consistent field and singles and doubles configuration interaction spectroscopic data and dissociation energies for the diatomics B2, C2, N2, O2, F2, CN, CP, CS, PN, SiC, SiN, SiO, SiP, and their ions

    NASA Astrophysics Data System (ADS)

    McLean, A. D.; Liu, B.; Chandler, G. S.

    1992-12-01

    Results are presented for single-configuration self-consistent field (SCF) calculations near the Hartree-Fock limit. Singles and doubles configuration-interaction calculations from this single SCF configuration were performed for the ground states and selected excited states of the molecules B2, B2(+), C2, C2(+), N2, N2(+), O2, O2(+), F2, F2(+), CN, CN(-), CP, CS, PN, SiC, SiC(-), SiN, SiN(-), SiO, and SiP. Results include potential energy curves, equilibrium bond lengths, vibrational energies, ionization potentials, and dissociation energies.

  4. Steady-state radiolysis and product analysis of aqueous diphenyloxide in the presence of air and N 2O

    NASA Astrophysics Data System (ADS)

    Popov, P.; Getoff, N.; Grodkowski, J.; Zimek, Z.; Chmielewski, A. G.

    2004-01-01

    The radiation-induced decomposition and product analysis of diphenyloxide (DPO; diphenylether), selected as a representative of the toxic polyaromatic, volatile, hydrocarbons produced by combustion of coal, was investigated in aqueous solution. In the presence of air an initial degradation yield, Gi(-DPO)0=4.6 was obtained. Phenol ( Gi=1.3) appeared to be the major decomposition product in addition to a number of hydroxy-compounds as well as a mixture of aldehydes and carboxylic acids. DPO as well as the resulting products can be decomposed at an absorbed radiation dose of about 5 kGy. By performing analogous studies in solution saturated with N 2O an initial yield of Gi(-DPO)=5.0 and similar radiolytic products were found. Again phenol ( Gi=1.5) is observed as the main product. In this case a much lower radiation dose (˜2.5 kGy) is found to be sufficient for the decomposition of DPO and its radiolytic products. Most likely reaction mechanisms are presented for explanation of the observed products.

  5. DNA oxidatively damaged by chromium(III) and H(2)O(2) is protected by the antioxidants melatonin, N(1)-acetyl-N(2)-formyl-5-methoxykynuramine, resveratrol and uric acid.

    PubMed

    Burkhardt, S; Reiter, R J; Tan, D X; Hardeland, R; Cabrera, J; Karbownik, M

    2001-08-01

    Chromium (Cr) compounds are widely used industrial chemicals and well known carcinogens. Cr(III) was earlier found to induce oxidative damage as documented by examining the levels of 8-hydroxydeoxyguanosine (8-OH-dG), an index for DNA damage, in isolated calf thymus DNA incubated with CrCl(3) and H(2)O(2). In the present in vitro study, we compared the ability of the free radical scavengers melatonin, N(1)-acetyl-N(2)-formyl-5-methoxykynuramine (AFMK), resveratrol and uric acid to reduce DNA damage induced by Cr(III). Each of these scavengers markedly reduced the DNA damage in a concentration-dependent manner. The concentrations that reduced 8-OH-dG formation by 50% (IC(50)) were 0.10 microM for both resveratrol and melatonin, and 0.27 microM for AFMK. However, the efficacy of the fourth endogenous antioxidant, i.e. uric acid, in terms of its inhibition of DNA damage in the same in vitro system was about 60--150 times less effective than the other scavengers; the IC(50) for uric acid was 15.24 microM. These findings suggest that three of the four antioxidants tested in these studies may have utility in protecting against the environmental pollutant Cr and that the protective effects of these free radical scavengers against Cr(III)-induced carcinogenesis may relate to their direct hydroxyl radical scavenging ability. In the present study, the formation of 8-OH-dG was likely due to a Cr(III)-mediated Fenton-type reaction that generates hydroxyl radicals, which in turn damage DNA. Once formed, 8-OH-dG can mutate eventually leading to cancer; thus the implication is that these antioxidants may reduce the incidence of Cr-related cancers.

  6. Ozone generation in a kHz-pulsed He-O2 capillary dielectric barrier discharge operated in ambient air

    NASA Astrophysics Data System (ADS)

    Sands, Brian L.; Ganguly, Biswa N.

    2013-12-01

    The generation of reactive oxygen species using nonequilibrium atmospheric pressure plasma jet devices has been a subject of recent interest due to their ability to generate localized concentrations from a compact source. To date, such studies with plasma jet devices have primarily utilized radio-frequency excitation. In this work, we characterize ozone generation in a kHz-pulsed capillary dielectric barrier discharge configuration comprised of an active discharge plasma jet operating in ambient air that is externally grounded. The plasma jet flow gas was composed of helium with an admixture of up to 5% oxygen. A unipolar voltage pulse train with a 20 ns pulse risetime was used to drive the discharge at repetition rates between 2-25 kHz. Using UVLED absorption spectroscopy centered at 255 nm near the Hartley-band absorption peak, ozone was detected over 1 cm from the capillary axis. We observed roughly linear scaling of ozone production with increasing pulse repetition rate up to a "turnover frequency," beyond which ozone production steadily dropped and discharge current and 777 nm O(5P→5S°) emission sharply increased. The turnover in ozone production occurred at higher pulse frequencies with increasing flow rate and decreasing applied voltage with a common energy density of 55 mJ/cm3 supplied to the discharge. The limiting energy density and peak ozone production both increased with increasing O2 admixture. The power dissipated in the discharge was obtained from circuit current and voltage measurements using a modified parallel plate dielectric barrier discharge circuit model and the volume-averaged ozone concentration was derived from a 2D ozone absorption measurement. From these measurements, the volume-averaged efficiency of ozone production was calculated to be 23 g/kWh at conditions for peak ozone production of 41 mg/h at 11 kV applied voltage, 3% O2, 2 l/min flow rate, and 13 kHz pulse repetition rate, with 1.79 W dissipated in the discharge.

  7. Synthesis of hectorite-TiO2 and kaolinite-TiO2 nanocomposites with photocatalytic activity for the degradation of model air pollutants

    SciTech Connect

    Destaillats, Hugo; Kibanova, D.; Trejo, M.; Destaillats, H.; Cervini-Silva, J.

    2008-03-01

    We studied the synthesis and photocatalytic activity of small-sized TiO{sub 2} supported on hectorite and kaolinite. Deposition of TiO{sub 2} on the clay mineral surface was conducted by using a sol-gel method with titanium isopropoxide as precursor. Anatase TiO{sub 2} particles formation was achieved by hydrothermal treatment at 180 C. Material characterization was conducted using XRD, SEM, XPS, ICP-OES, BET and porosimetry analysis. Efficiency in synthesizing clay-TiO{sub 2} composites depended strongly on the clay mineral structure. Incorporation of anatase in hectorite, an expandable clay mineral, was found to be very significant (> 36 wt.% Ti) and to be followed by important structural changes at the clay mineral surface. Instead, no major structural modifications of the clay were observed for kaolinite-TiO{sub 2}, as compared with the untreated material. Photocatalytic performance of clay-TiO{sub 2} composites was evaluated with ATR-FTIR following the oxidation of adsorbed toluene and d-limonene, two model air pollutants. In either case, the photocatalytic removal efficiency of these hydrophobic substrates by the synthesized clay-TiO{sub 2} composites was comparable to that observed using pure commercial TiO{sub 2} (Degussa P25).

  8. Selective adsorption of thiophenic compounds from fuel over TiO2/SiO2 under UV-irradiation.

    PubMed

    Miao, Guang; Ye, Feiyan; Wu, Luoming; Ren, Xiaoling; Xiao, Jing; Li, Zhong; Wang, Haihui

    2015-12-30

    This study investigates selective adsorption of thiophenic compounds from fuel over TiO2/SiO2 under UV-irradiation. The TiO2/SiO2 adsorbents were prepared and then characterized by N2 adsorption, X-ray diffraction and X-ray photoelectron spectroscopy. Adsorption isotherms, selectivity and kinetics of TiO2/SiO2 were measured in a UV built-in batch reactor. It was concluded that (a) with the employment of UV-irradiation, high organosulfur uptake of 5.12 mg/g was achieved on the optimized 0.3TiO2/0.7SiO2 adsorbent at low sulfur concentration of 15 ppmw-S, and its adsorption selectivity over naphthalene was up to 325.5; (b) highly dispersed TiO2 served as the photocatalytic sites for DBT oxidation, while SiO2 acted as the selective adsorption sites for the corresponding oxidized DBT using TiO2 as a promoter, the two types of active sites worked cooperatively to achieve the high adsorption selectivity of TiO2/SiO2; (c) The kinetic rate-determining step for the UV photocatalysis-assisted adsorptive desulfurization (PADS) over TiO2/SiO2 was DBT oxidation; (d) consecutive adsorption-regeneration cycles suggested that the 0.3TiO2/0.7SiO2 adsorbent can be regenerated by acetonitrile washing followed with oxidative air treatment. This work demonstrated an effective PADS approach to greatly enhance adsorption capacity and selectivity of thiophenic compounds at low concentrations for deep desulfurization under ambient conditions.

  9. Semi-rechargeable Aluminum-Air Battery with a TiO2 Internal Layer with Plain Salt Water as an Electrolyte

    NASA Astrophysics Data System (ADS)

    Mori, Ryohei

    2016-07-01

    To develop a semi-rechargeable aluminum-air battery, we attempted to insert various kinds of ceramic oxides between an aqueous NaCl electrolyte and an aluminum anode. From cyclic voltammetry experiments, we found that some of the ceramic oxide materials underwent an oxidation-reduction reaction, which indicates the occurrence of a faradaic electrochemical reaction. Using a TiO2 film as an internal layer, we successfully prepared an aluminum-air battery with secondary battery behavior. However, cell impedance increased as the charge/discharge reactions proceeded probably because of accumulation of byproducts in the cell components and the air cathode. Results of quantum calculations and x-ray photoelectron spectroscopy suggest the possibility of developing an aluminum rechargeable battery using TiO2 as an internal layer.

  10. S(p)O(2) values in acute medical admissions breathing air--implications for the British Thoracic Society guideline for emergency oxygen use in adult patients?

    PubMed

    Smith, Gary B; Prytherch, David R; Watson, Duncan; Forde, Val; Windsor, Alastair; Schmidt, Paul E; Featherstone, Peter I; Higgins, Bernie; Meredith, Paul

    2012-10-01

    S(p)O(2) is routinely used to assess the well-being of patients, but it is difficult to find an evidence-based description of its normal range. The British Thoracic Society (BTS) has published guidance for oxygen administration and recommends a target S(p)O(2) of 94-98% for most adult patients. These recommendations rely on consensus opinion and small studies using arterial blood gas measurements of saturation (S(a)O(2)). Using large datasets of routinely collected vital signs from four hospitals, we analysed the S(p)O(2) range of 37,593 acute general medical inpatients (males: 47%) observed to be breathing room air. Age at admission ranged from 16 to 105 years with a mean (SD) of 64 (21) years. 19,642 admissions (52%) were aged <70 years. S(p)O(2) ranged from 70% to 100% with a median (IQR) of 97% (95-98%). S(p)O(2) values for males and females were similar. In-hospital mortality for the study patients was 5.27% (range 4.80-6.27%). Mortality (95% CI) for patients with initial S(p)O(2) values of 97%, 96% and 95% was 3.65% (3.22-4.13); 4.47% (3.99-5.00); and 5.67% (5.03-6.38), respectively. Additional analyses of S(p)O(2) values for 37,299 medical admissions aged ≥18 years provided results that were distinctly different to those upon which the current BTS guidelines based their definition of normality. Our findings suggest that the BTS should consider changing its target saturation for actively treated patients not at risk of hypercapnic respiratory failure to 96-98%.

  11. ABA induces H2O2 production in guard cells, but does not close the stomata on Vicia faba leaves developed at high air humidity.

    PubMed

    Arve, Louise E; Carvalho, Dália R A; Olsen, Jorunn E; Torre, Sissel

    2014-01-01

    Plants developed under constant high (> 85%) relative air humidity (RH) have larger stomata that are unable to close completely. One of the hypotheses for the less responsive stomata is that the plants have reduced sensitivity to abscisic acid (ABA). Both ABA and darkness are signals for stomatal closure and induce the production of the secondary messenger hydrogen peroxide (H2O2). In this study, the ability of Vicia faba plants developed in moderate or high RH to close the stomata in response to darkness, ABA and H2O2 was investigated. Moreover, the ability of the plants to produce H2O2 when treated with ABA or transferred to darkness was also assessed. Our results show that the ABA concentration in moderate RH is not increased during darkness even though the stomata are closing. This indicates that stomatal closure in V. faba during darkness is independent of ABA production. ABA induced both H2O2 production and stomatal closure in stomata formed at moderate RH. H2O2 production, as a result of treatment with ABA, was also observed in stomata formed at high RH, though the closing response was considerably smaller as compared with moderate RH. In either RH, leaf ABA concentration was not affected by darkness. Similarly to ABA treatment, darkness elicited both H2O2 production and stomatal closure following plant cultivation at moderate RH. Contrary to this, neither H2O2 production nor stomatal closure took place when stomata were formed at high RH. These results suggest that the reduced stomatal response in plants developed in continuous high RH is caused by one or more factors downstream of H2O2 in the signaling pathway toward stomatal closure.

  12. ABA induces H2O2 production in guard cells, but does not close the stomata on Vicia faba leaves developed at high air humidity

    PubMed Central

    Arve, Louise E; Carvalho, Dália RA; Olsen, Jorunn E; Torre, Sissel

    2014-01-01

    Plants developed under constant high (> 85%) relative air humidity (RH) have larger stomata that are unable to close completely. One of the hypotheses for the less responsive stomata is that the plants have reduced sensitivity to abscisic acid (ABA). Both ABA and darkness are signals for stomatal closure and induce the production of the secondary messenger hydrogen peroxide (H2O2). In this study, the ability of Vicia faba plants developed in moderate or high RH to close the stomata in response to darkness, ABA and H2O2 was investigated. Moreover, the ability of the plants to produce H2O2 when treated with ABA or transferred to darkness was also assessed. Our results show that the ABA concentration in moderate RH is not increased during darkness even though the stomata are closing. This indicates that stomatal closure in V. faba during darkness is independent of ABA production. ABA induced both H2O2 production and stomatal closure in stomata formed at moderate RH. H2O2 production, as a result of treatment with ABA, was also observed in stomata formed at high RH, though the closing response was considerably smaller as compared with moderate RH. In either RH, leaf ABA concentration was not affected by darkness. Similarly to ABA treatment, darkness elicited both H2O2 production and stomatal closure following plant cultivation at moderate RH. Contrary to this, neither H2O2 production nor stomatal closure took place when stomata were formed at high RH. These results suggest that the reduced stomatal response in plants developed in continuous high RH is caused by one or more factors downstream of H2O2 in the signaling pathway toward stomatal closure. PMID:25763494

  13. Reactive uptake coefficients for N2O5 determined from aircraft measurements during the Second Texas Air Quality Study: Comparison to current model parameterizations

    NASA Astrophysics Data System (ADS)

    Brown, Steven S.; Dubé, William P.; Fuchs, Hendrik; Ryerson, Thomas B.; Wollny, Adam G.; Brock, Charles A.; Bahreini, Roya; Middlebrook, Ann M.; Neuman, J. Andrew; Atlas, Elliot; Roberts, James M.; Osthoff, Hans D.; Trainer, Michael; Fehsenfeld, Frederick C.; Ravishankara, A. R.

    2009-04-01

    This paper presents determinations of reactive uptake coefficients for N2O5, γ(N2O5), on aerosols from nighttime aircraft measurements of ozone, nitrogen oxides, and aerosol surface area on the NOAA P-3 during Second Texas Air Quality Study (TexAQS II). Determinations based on both the steady state approximation for NO3 and N2O5 and a plume modeling approach yielded γ(N2O5) substantially smaller than current parameterizations used for atmospheric modeling and generally in the range 0.5-6 × 10-3. Dependence of γ(N2O5) on variables such as relative humidity and aerosol composition was not apparent in the determinations, although there was considerable scatter in the data. Determinations were also inconsistent with current parameterizations of the rate coefficient for homogenous hydrolysis of N2O5 by water vapor, which may be as much as a factor of 10 too large. Nocturnal halogen activation via conversion of N2O5 to ClNO2 on chloride aerosol was not determinable from these data, although limits based on laboratory parameterizations and maximum nonrefractory aerosol chloride content showed that this chemistry could have been comparable to direct production of HNO3 in some cases.

  14. Liquidus Measurement of Te-O-Na2O-SiO2 System Between 1000 and 1200 °C in Equilibrium with Air

    NASA Astrophysics Data System (ADS)

    Santoso, Imam; Taskinen, Pekka

    Thermodynamic properties of Te-O-Na2O-SiO2 system at high temperatures are essential for improving the metallurgical processes especially for smelting the anode slime which contains tellurium compounds. However, the literatures review of previous investigation, showed that there are no liquidus data reported for this system. In the present study the experimental data were obtained by equilibrating the high purity of oxide mixtures at selected temperature, followed by rapid quenching of the equilibrated samples in cold water and compositional analysis using electron probe X-ray microanalyzer. Phase characteristic and the liquidus in the Te-O-Na2O-SiO2 system have been investigated at silica saturation between 1000 and 1200 °C in equilibrium with air. New data sets of the liquidus in the Te-O-Na2O-SiO2 system have been generated and evaluated.

  15. A critical review of macroscopic modeling studies on Li O2 and Li-air batteries using organic electrolyte: Challenges and opportunities

    NASA Astrophysics Data System (ADS)

    Li, Xianglin; Huang, Jing; Faghri, Amir

    2016-11-01

    A comprehensive review of the state-of-the-art macroscopic modeling studies on lithium oxygen (Li O2) and lithium air (Li-air) batteries has been presented. The Li O2 battery is a promising device for energy storage in portable electronics and electric vehicles due to its high specific energy. A number of technical challenges need to be addressed in order to bring this technology from laboratory concept to real products. The multi-scale, multi-physics phenomena in a Li O2 battery encompasses a wide range of scientific disciplines, including electrochemistry, heat and mass transfer, and material science. Modeling study provides a powerful tool to understand the charge-species transport phenomena inside a battery that cannot be captured by experimentation. It offers insight to optimize battery design and fabrication. Macroscopic models that treat battery components as continuous media will be the focus of this review while pore-scale sub-models that are integrated with macroscopic models to describe structural changes of battery components (mainly electrodes) will be presented and compared as well. Recent developments and opportunities for future improvement and advancement are also discussed. Finally, a detailed summary of property data relevant to Li O2 batteries is provided because of their critical role in modeling studies.

  16. Changes in Sugars, Enzymic Activities and Acid Phosphatase Isoenzyme Profiles of Bananas Ripened in Air or Stored in 2.5% O2 with and without Ethylene 1

    PubMed Central

    Kanellis, Angelos K.; Solomos, Theophanes; Mattoo, Autar K.

    1989-01-01

    This study investigates the effect of 2.5% O2, both alone and in combination with ethylene, on respiration, sugar accumulation and activities of pectin methylesterase and acid phosphatase during ripening of bananas (Musa paradisiaca sapientum). In addition, the changes in the phosphatase isoenzyme profiles are also analyzed. Low oxygen diminished respiration and slowed down the accumulation of sugars and development of the yellow color. Furthermore, low O2 prevented the rise in acid phosphatase activities and this suppression was not reversed by the inclusion of 100 microliters per liter ethylene in 2.5% O2 atmosphere. Gel electrophoresis of both the soluble and particulate cell-free fractions under nondenaturing conditions revealed the presence of 8 and 9 isoenzymes in the soluble and particulate fractions, respectively. Low O2 suppressed the appearance of all isoenzymes, and the addition of 500 microliters per liter ethylene to the low oxygen atmosphere did not reverse this effect. Similarly, the decline in pectin methylesterase that was observed in air-ripened fruits was prevented by 2.5% O2 alone and in combination with 500 microliters per liter ethylene. Images Figure 5 Figure 6 Figure 7 PMID:16666745

  17. Performance enhancement of an experimental air conditioning system by using TiO2/methanol nanofluid in heat pipe heat exchangers

    NASA Astrophysics Data System (ADS)

    Monirimanesh, Negin; Nowee, S. Mostafa; Khayyami, Shideh; Abrishamchi, Iman

    2016-05-01

    The effect of using nanofluid in thermosyphon-type heat pipe heat exchangers on energy conservation of an air-conditioning system was sought in this study. Innovatively, two heat exchangers in-series were deployed using TiO2/methanol nanofluids with 0-4 wt% concentrations as working fluids. The impacts of temperature and relative humidity on the effectiveness of 2 and 4-row heat exchangers were analyzed experimentally and more that 40 % energy saving was obtained.

  18. Impact of air exposure and annealing on the chemical and electronic properties of the surface of SnO2 nanolayers deposited by rheotaxial growth and vacuum oxidation

    PubMed Central

    Krzywiecki, Maciej

    2017-01-01

    In this paper the SnO2 nanolayers were deposited by rheotaxial growth and vacuum oxidation (RGVO) and analyzed for the susceptibility to ambient-air exposure and the subsequent recovery under vacuum conditions. Particularly the surface chemistry of the layers, stoichiometry and level of carbon contamination, was scrutinized by X-ray photoelectron spectroscopy (XPS). The layers were tested i) pristine, ii) after air exposure and iii) after UHV annealing to validate perspective recovery procedures of the sensing layers. XPS results showed that the pristine RGVO SnO2 nanolayers are of high purity with a ratio [O]/[Sn] = 1.62 and almost no carbon contamination. After air exposure the relative [O]/[Sn] concentration increased to 1.80 while maintaining a relatively low level of carbon contaminants. Subsequent UHV annealing led to a relative [O]/[Sn] concentration comparable to the pristine samples. The oxidation resulted in a variation of the distance between the valence band edge and the Fermi level energy. This was attributed to oxygen diffusion through the porous SnO2 surface as measured by atomic force microscopy. PMID:28382240

  19. Measurements of N2O and SF6 mole fraction between 1977 and 1998 in archived air samples from Cape Meares, Oregon

    NASA Astrophysics Data System (ADS)

    Rolfe, T.; Rice, A. L.; Radda, J.

    2015-12-01

    The quantification of greenhouse gas concentrations in the atmosphere is important for monitoring imbalances in their global budgets between sources and sinks and their changes in time. Nitrous oxide (N2O) is a strong radiative trace gas with a GWP of ~300 times CO2 over a 100 year period and an atmospheric lifetime of ~100 years. The preindustrial revolution background concentration of N2O was ~270 ppb. Today, the concentration is ~330 ppb. Sulfur hexafluoride (SF6) is another potent greenhouse gas with a long lifetime (800 to 3200 years) and very large GWP (~23000 times CO2 over a 100 year period). Its current atmospheric concentration is low (~8 ppt today). Direct measurements of N2O and SF6 in air prior to the mid-1990s are few. Over 200 archived atmospheric gas samples collected at Cape Meares, Oregon between 1977 and 1998 were analyzed for their N2O and SF6 concentrations using an Agilent (model 6890 N) gas chromatograph fitted with an electron capture detector using a two column "heart-cut" technique. Precision of measurement of N2O and SF6 is calculated at 0.13% (1σ) and 1.35% (1σ) respectively. N2O concentrations in the late 1970s and early 1980s average around 303 ppb, rising to 309 ppb in the early 1990s. Between 1980 and 1990, the increase in N2O concentrations is found to be ~0.5 ppb/yr. SF6 concentrations during the late 1970s and early 1980s average around 0.9 ppt and rise slowly, reaching 1.6 ppt in the 1990s. We find that the increase in SF6 between 1980 and 1990 to be ~0.07 ppt/yr. We also discuss sample integrity in storage and observed temporal trends of N2O and SF6.

  20. High-Precision Measurement of The Oxygen Isotopic Composition of Tropospheric O2: Implications for Δ17O of air as a Biosignature

    NASA Astrophysics Data System (ADS)

    Young, E. D.; Ziegler, K.

    2006-05-01

    Here we present high-precision measurements of 18O/16O and 17O/16O in samples of tropospheric O2 using a standard calibrated with measurements of terrestrial and extraterrestrial rock samples. These new data provide a measure of Δ17O on an absolute scale that aids in the interpretation of the cause of the disparity in Δ17O between O2 in the troposphere and terrestrial rocks. We measured the isotopic composition of four separate aliquotes of ground-level air O2. Oxygen was isolated from air cryogenically using molecular sieve substrates. Correction was made for the influence of Ar scattered across the Faraday collectors (~0.06 per mil in δ17O) of the gas- source mass spectrometer. The reference gas used as an internal standard was calibrated against terrestrial rock samples and meteorites analyzed using infrared laser heating fluorination. All results are reported as linearized delta values (signified with a prime superscript symbol). With a mean terrestrial rock Δ17O'of 0.00 ‰ ± 0.02 we obtain Δ17O values of -0.25 ‰ ± 0.04 1σ, -0.22 ‰ ± 0.03, and -0.23 ‰ ± 0.05 for 5 mesosiderite meteorites, 7 pallasites, and 12 HED meteorites, respectively. The latter meteorite data are consistent with results from three other laboratories and serve to establish the absolute scale for the air O2 measurements. Our results for the O2 samples give a mean linearized δ18O' of 23.237 ‰ ± 0.008 1 std err (corresponding to a normal, non-linearized δ18O SMOW value of 23.509 ‰), a mean δ17O' of 11.922 ‰ ± 0.018, and a mean linearized Δ17O' of -0.347 ‰ ± 0.018 based on a rock-water terrestrial fractionation reference line with a slope (β) of 0.528. The latter is the exponent in a normal fractionation law described by the relation α17=(α18)β. This result can be reconciled with the suggestion by Young et al (2002) that the whole of the departure in Δ17O' of tropospheric O2 relative to terrestrial rocks can be attributed to respiration (a Δ17O Dole effect

  1. Performance of air plasma spraying parameters in the fabrication of ZrO2-10%Y2O3-18% TiO2 thermal barrier coatings

    NASA Astrophysics Data System (ADS)

    Liscano, S.; Gil, L.

    2013-11-01

    In this research, ZrO2-10%Y2O3-18% TiO2 thermal barrier coatings (TBCs) were sprayed by employing an air plasma thermal spray (APS) technique following a 23 factorial design experiment in order to obtain the best favorable spraying conditions able to enhance their properties. The effect of the spraying parameters on the porosity, microhardness, microstructure and morphology were determined by using different techniques such as optical microscopy (OP), image analysis, Vickers indentation and scanning electron microscopy (SEM) technique, this latter coupled with X-Ray microanalysis (EDS). It was found that both the arc voltage and the powder feed rate, as well as their interaction had a significant effect on the values of the reported hardness and these results were related to the existing level of porosity in the coatings. It was concluded that the best coatings properties, for the level of the variables studied in this work, could be obtained if the arc voltage is maintained at 36 V, the arc current at 900 A and the powder feed rate to 24 g/min.

  2. Phase Equilibria Study in the TeO2-Na2O-SiO2 System in Air Between 723 K (500 °C) and 1473 K (1200 °C)

    NASA Astrophysics Data System (ADS)

    Santoso, Imam; Taskinen, Pekka

    2016-08-01

    Knowledge of phase equilibria in the TeO2-Na2O-SiO2 system at elevated temperatures is important for ceramic and glass industries and for improving the operation of the smelting process of tellurium-containing materials. A review of previous investigations has indicated, however, that there are omissions in the available datasets on the liquidus temperatures of the molten TeO2-Na2O-SiO2 mixtures. The employed experimental method included equilibration of mixtures made from high purity oxides, rapid quenching of the equilibrated samples in water and followed by compositional analysis of the phases using an electron probe X-ray microanalyzer. The liquidus and phase equilibria in the TeO2-SiO2, TeO2-Na2O, and SiO2-TeO2-Na2O systems have been studied for a wide range of compositions between 723 K (500 °C) and 1473 K (1200 °C) at TeO2, SiO2, and Na2SiO3 saturations. New data have been generated in the SiO2-TeO2-Na2O system at SiO2 saturation. The liquidus compositions in the TeO2-Na2O system at TeO2 saturation have been compared with the previous data and an assessed phase diagram.

  3. Effect of Au clustering on ferromagnetism in Au doped TiO2 films: theory and experiments investigation

    NASA Astrophysics Data System (ADS)

    Zou, Zhaorui; Zhou, Zhongpo; Wang, Haiying; Yang, Zongxian

    2017-01-01

    In this paper, we investigated the physical properties especially the magnetic properties of the TiO2 films and Au cluster doped TiO2 films fabricated by sol-gel and sputtering methods combined experiments and first-principles calculations. All the samples annealed under air and N2 atmosphere respectively exhibit room temperature ferromagnetism with the crystal phase of anatase. The values of the saturation magnetizations are in the order of Au δ-doped TiO2 (annealed in N2)>undoped TiO2 (annealed in air)>Au δ-doped TiO2 (annealed in air). The first principles calculation results show that the formation energy of Au cluster doped TiO2 films is lower than that of the oxygen vacancy and Au cluster codoped TiO2 films. The effects of the Au cluster dopant are the retard of the formation of surface oxygen vacancy and the electrons transfer from 3d states of Ti atoms to Au 5d states in Au cluster doped TiO2 films. The codoping of surface oxygen vacancies, bulk oxygen vacancies and Au clusters led to the spin-split of Ti 3d and O 2p in Au cluster doped TiO2 films (annealed in N2) which yield the highest saturation magnetization.

  4. Determination of CH4, CO2 and N2O in air samples and soil atmosphere by gas chromatography mass spectrometry, GC-MS.

    PubMed

    Ekeberg, Dag; Ogner, Gunnar; Fongen, Monica; Joner, Erik J; Wickstrom, Torild

    2004-07-01

    A method for determination of the climate gases CH4, CO2 and N2O in air samples and soil atmosphere was developed using GC-MS. The method uses straightforward gas chromatography (separation of the gases) with a mass spectrometric detector in single ion mode (specific determination). The gases were determined with high sensitivity and high sample throughput (18 samples h(-1)). The LOD (3sigma) for the gases were 0.10 micro L L(-1) for CH4, 20 microL L(-1) for CO2 and 0.02 microL L(-1) for N2O. The linear range (R2 = 0.999) was up to 500 microL L(-1) for CH4, 4000 microL L(-1) for CO2 and 80 microL L(-1) for N2O. The samples were collected in 10 mL vials and a 5 microL aliquot was injected on column. The method was tested against certified gas references, the analytical data gave an accuracy within +/-5% and a precision of +/-3%. The presence of < or = 10% by volume of C2H2 (often used experimentally to prevent N2 formation from N2O) did not interfere with detection for the targeted trace gases.

  5. Catalytic evaluation on liquid phase oxidation of vanillyl alcohol using air and H2O2 over mesoporous Cu-Ti composite oxide

    NASA Astrophysics Data System (ADS)

    Saha, Subrata; Hamid, Sharifah Bee Abd; Ali, Tammar Hussein

    2017-02-01

    A mesoporous, highly crystalline Cu-Ti composite oxide catalyst was prepared via facile, simple and modified solution method varying Cu and Ti ratio for selective liquid phase oxidation of vanillyl alcohol. Various spectroscopic procedures were employed to systematically characterize the catalyst structural and physicochemical properties. The defect chemistry of the catalyst was confirmed from the presence of surface defects revealed through HRTEM imagery between the TiO2 (101) and Cu3TiO4 (012) planes, complemented by the XRD profiling. Further, presence of oxygen vacancy evidenced by O 1s XPS spectra were observed on the catalyst surface. Moreover, the stoichiometry of Cu and Ti in the catalyst synthesis protocol was notably found to be the vital determinant to alter the redox properties of Cu-Ti composite oxide catalyst supported by H2-TPR. O2-TPD analysis. Moreover, a rational investigation was done using different oxidants such as air and H2O2 with variables reaction conditions. The catalyst was active for liquid phase oxidation of vanillyl alcohol to vanillin with performance of 66% conversion and 71% selectivity using H2O2 in base free condition. And also, catalytic activity was significantly improved by 94% conversion with 86% selectivity to vanillin in liquid phase aerobic oxidation at the optimum reaction conditions. To expand the superiority of the catalyst, three times reusability study was also examined with appreciable catalytic activity.

  6. A selected ion flow tube study of the reactions of NO + and O + 2 ions with some organic molecules: The potential for trace gas analysis of air

    NASA Astrophysics Data System (ADS)

    Španěl, Patrik; Smith, David

    1996-02-01

    A study has been carried out using our selected ion flow tube apparatus of the reactions of NO+ and O+2 ions in their vibronic ground states with ten organic species: the hydrocarbons, benzene, toluene, isoprene, cyclopropane, and n-pentane; the oxygen-containing organics, methanol, ethanol, acetaldehyde, acetone, and diethyl ether. The major objectives of this work are, on the one hand, to fully understand the processes involved in these reactions and, on the other hand, to explore the potential of NO+ and O+2 as chemical ionization agents for the analysis of trace gases in air and on human breath. Amongst the NO+ reactions, charge transfer, hydride-ion transfer, and termolecular association occur, and the measured rate coefficients, k, for the reactions vary from immeasurably small to the maximum value, collisional rate coefficient, kc. The O+2 reactions are all fast, in each case the k being equal to or an appreciable fraction of kc, and charge transfer producing the parent organic ion or dissociative charge transfer resulting in two or three fragments of the parent ion are the reaction processes that occur. We conclude from these studies, and from previous studies, that NO+ ions and O+2 ions can be used to great effect as chemical ionization agents for trace gas analysis, especially in combination with H3O+ ions which we now routinely use for this purpose.

  7. The Influence of Carbonaceous Matrices and Electrocatalytic MnO2 Nanopowders on Lithium-Air Battery Performances

    PubMed Central

    Minguzzi, Alessandro; Longoni, Gianluca; Cappelletti, Giuseppe; Pargoletti, Eleonora; Di Bari, Chiara; Locatelli, Cristina; Marelli, Marcello; Rondinini, Sandra; Vertova, Alberto

    2016-01-01

    Here, we report new gas diffusion electrodes (GDEs) prepared by mixing two different pore size carbonaceous matrices and pure and silver-doped manganese dioxide nanopowders, used as electrode supports and electrocatalytic materials, respectively. MnO2 nanoparticles are finely characterized in terms of structural (X-ray powder diffraction (XRPD), energy dispersive X-ray (EDX)), morphological (SEM, high-angle annular dark field (HAADF)-scanning transmission electron microscopy (STEM)/TEM), surface (Brunauer Emmet Teller (BET)-Barrett Joyner Halenda (BJH) method) and electrochemical properties. Two mesoporous carbons, showing diverse surface areas and pore volume distributions, have been employed. The GDE performances are evaluated by chronopotentiometric measurements to highlight the effects induced by the adopted materials. The best combination, hollow core mesoporous shell carbon (HCMSC) with 1.0% Ag-doped hydrothermal MnO2 (M_hydro_1.0%Ag) allows reaching very high specific capacity close to  1400 mAh·g−1. Considerably high charge retention through cycles is also observed, due to the presence of silver as a dopant for the electrocatalytic MnO2 nanoparticles. PMID:28344267

  8. Determination of the rate coefficients for the reactions IO + NO2 + M (air) --> IONO2 + M and O(3P) + NO2 --> O2 + NO using laser-induced fluorescence spectroscopy.

    PubMed

    Dillon, Terry J; Blitz, Mark A; Heard, Dwayne E

    2006-06-01

    Laser-induced fluorescence spectroscopy via excitation of the A2pi(3/2) <-- X2pi(3/2) (2,0) band at 445 nm was used to monitor IO in the presence of NO2 following its generation in the reactions O(3P) + CF3I and O(3P) + I2. Both photolysis of O3 (248 nm) and NO2 (351 nm) were used to initiate the production of IO. The rate coefficients for the thermolecular reaction IO + NO2 + M --> IONO2 + M were measured in air, N2, and O2 over the range P = 18-760 Torr, covering typical tropospheric conditions, and were found to be in the falloff region. No dependence of k1 upon bath gas identity was observed, and in general, the results are in good agreement with recent determinations. Using a Troe broadening factor of F(B) = 0.4, the falloff parameters k0(1) = (9.5 +/- 1.6) x 10(-31) cm6 molecule(-2) s(-1) and k(infinity)(1) = (1.7 +/- 0.3) x 10(-11) cm3 molecule(-1) s(-1) were determined at 294 K. The temporal profile of IO at elevated temperatures was used to investigate the thermal stability of the product, IONO2, but no evidence was observed for the regeneration of IO, consistent with recent calculations for the IO-NO2 bond strength being approximately 100 kJ mol(-1). Previous modeling studies of iodine chemistry in the marine boundary layer that utilize values of k1 measured in N2 are hence validated by these results conducted in air. The rate coefficient for the reaction O(3P) + NO2 --> O2 + NO at 294 K and in 100 Torr of air was determined to be k2 = (9.3 +/- 0.9) x 10(-12) cm3 molecule(-1) s(-1), in good agreement with recommended values. All uncertainties are quoted at the 95% confidence limit.

  9. Benefits and technological challenges in the implementation of TiO2-based ultraviolet photocatalytic oxidation (UVPCO) air cleaners

    SciTech Connect

    Hodgson, Al; Destaillats, Hugo; Hotchi, Toshifumi; Fisk, William J.

    2008-10-01

    Heating, ventilating, and cooling classrooms in California consume substantial electrical energy. Indoor air quality (IAQ) in classrooms affects student health and performance. In addition to airborne pollutants that are emitted directly by indoor sources and those generated outdoors, secondary pollutants can be formed indoors by chemical reaction of ozone with other chemicals and materials. Filters are used in nearly all classroom heating, ventilation and air-conditioning (HVAC) systems to maintain energy-efficient HVAC performance and improve indoor air quality; however, recent evidence indicates that ozone reactions with filters may, in fact, be a source of secondary pollutants. This project quantitatively evaluated ozone deposition in HVAC filters and byproduct formation, and provided a preliminary assessment of the extent to which filter systems are degrading indoor air quality. The preliminary information obtained will contribute to the design of subsequent research efforts and the identification of energy efficient solutions that improve indoor air quality in classrooms and the health and performance of students.

  10. Improved electrical properties of Ge metal-oxide-semiconductor capacitors with high-k HfO2 gate dielectric by using La2O3 interlayer sputtered with/without N2 ambient

    NASA Astrophysics Data System (ADS)

    Xu, H. X.; Xu, J. P.; Li, C. X.; Lai, P. T.

    2010-07-01

    The electrical properties of n-Ge metal-oxide-semiconductor (MOS) capacitors with HfO2/LaON or HfO2/La2O3 stacked gate dielectric (LaON or La2O3 as interlayer) are investigated. It is found that better electrical performances, including lower interface-state density, smaller gate leakage current, smaller capacitance equivalent thickness, larger k value, and negligible C-V frequency dispersion, can be achieved for the MOS device with LaON interlayer. The involved mechanism lies in that the LaON interlayer can effectively block the interdiffusions of Ge, O, and Hf, thus suppressing the growth of unstable GeOx interlayer and improving the dielectric/Ge interface quality.

  11. Engendering Long-Term Air and Light Stability of a TiO2-Supported Porphyrinic Dye via Atomic Layer Deposition.

    PubMed

    Hoffeditz, William L; Son, Ho-Jin; Pellin, Michael J; Farha, Omar K; Hupp, Joseph T

    2016-12-21

    Organic and porphyrin-based chromophores are prevalent in liquid-junction photovoltaic and photocatalytic solar-cell chemistry; however, their long-term air and light instability may limit their practicality in real world technologies. Here, we describe the protection of a zinc porphyrin dye, adsorbed on nanoparticulate TiO2, from air and light degradation by a protective coating of alumina grown with a previously developed post-treatment atomic layer deposition (ALD) technique. The protective Al2O3 ALD layer is deposited using dimethylaluminum isopropoxide as an Al source; in contrast to the ubiquitous ALD precursor trimethylaluminum, dimethylaluminum isopropoxide does not degrade the zinc porphyrin dye, as confirmed by UV-vis measurements. The growth of this protective ALD layer around the dye can be monitored by an in-reactor quartz crystal microbalance (QCM). Furthermore, greater than 80% of porphyrin light absorption is retained over ∼1 month of exposure to air and light when the protective coating is present, whereas almost complete loss of porphyrin absorption is observed in less than 2 days in the absence of the ALD protective layer. Applying the Al2O3 post-treatment technique to the TiO2-adsorbed dye allows the dye to remain in electronic contact with both the semiconductor surface and a surrounding electrolyte solution, the combination of which makes this technique promising for numerous other electrochemical photovoltaic and photocatalytic applications, especially those involving the dye-sensitized evolution of oxygen.

  12. Optical absorption in air/monolayer MoS2/S (Sdbnd SiO2 or Si) trilayer stacks at oblique incidence

    NASA Astrophysics Data System (ADS)

    Ansari, N.; Moradi, M.

    2017-04-01

    The monolayer MoS2 with strong light-matter interaction and optoelectronic properties is useful to design different optical devices such as photonic absorbers. In this paper, the MoS2 monolayer is sandwiched in the following stacks: SiO2/MoS2/air and Si/MoS2/air to study of increasing optical absorption. We study theoretically the absorption of these stacks as a function of polarization, incident angle and wavelength to reach the maximum value in the visible regime. The absorption intensity reaches to be as high as 65% for internal reflection and s polarization, around the blue wavelength for air/MoS2/SiO2 stack. Absorption behavior including maxima points as a function of wavelength is correlated with imaginary component of refractive index of the monolayer MoS2 except around critical angle. Our results recommend important role of internal and external reflection, cover and substrate layer, angle of incidence and polarization to design elements for optical energy harvesting applications.

  13. Incorporation of M(H2O)6(2+) between layers {M(H2O)2Ru2(CO3)4Cl2}n(2n-) (M = Zn, Mn): syntheses, structures and magnetic properties.

    PubMed

    Liu, Bin; Jia, Yan-Yan; Yang, Huai-Qing; Yang, Jian-Hui; Xue, Gang-Lin

    2013-12-28

    Isostructural heterometallic diruthenium carbonates KM(H2O)6[M(H2O)2Ru2(CO3)4Cl2]·4H2O [M = Zn (1) and Mn (2)] were synthesized from the reaction of the precursors [Ru2(CO3)4Cl2](5-) and transitional metal ions in aqueous solution. Complexes 1 and 2 show layered structures in which Ru2(II,III) units are linked by four octahedral environment M(H2O)2(2+) ions in a cross fashion and vice versa giving a negative bimetallic square grid layer {M(H2O)2Ru2(CO3)4Cl2}n(3n-). M(H2O)6(2+) ions, linked by K(+) forming zigzag chain {KM(H2O)6}n(3+), are located in the void spaces between the layers. The adjacent bimetallic carbonate layers are connected with K-O and K-Cl bonds, and hydrogen bonding, forming a supramolecular 3D framework structure. Their magnetic properties were characterized in detail, and intralayer ferromagnetic coupling between the Ru2 dimer and Mn(2+) ion, as well as long-range ordering (Tc = 5.2 K) coexistence of domain movement behavior were observed for complex 2.

  14. Water absorption lines, 931-961 nm - Selected intensities, N2-collision-broadening coefficients, self-broadening coefficients, and pressure shifts in air

    NASA Technical Reports Server (NTRS)

    Giver, L. P.; Gentry, B.; Schwemmer, G.; Wilkerson, T. D.

    1982-01-01

    Intensities were measured for 97 lines of H2O vapor between 932 and 961 nm. The lines were selected for their potential usefulness for remote laser measurements of H2O vapor in the earth's atmosphere. The spectra were obtained with several different H2O vapor abundances and N2 broadening gas pressures; the spectral resolution was 0.046/cm FWHM. Measured H2O line intensities range from 7 x 10 to the -25th to 7 x 10 to the -22nd/cm per (molecules/sq cm). H2O self-broadening coefficients were measured for 13 of these strongest lines; the mean value was 0.5/cm per atm. N2-collision-broadening coefficients were measured for 73 lines, and the average was 0.11 cm per atm HWHM. Pressure shifts in air were determined for a sample of six lines between 948 and 950 nm; these lines shift to lower frequency by an amount comparable to 0.1 of the collision-broadened widths measured in air or N2. The measured intensities of many lines of 300-000 band are much larger than expected from prior computations, in some cases by over an order of magnitude. Coriolis interactions with the stronger 201-000 band appear to be the primary cause of the enhancement of these line intensities.

  15. One-pot synthesis of La0.7Sr0.3MnO3 supported on flower-like CeO2 as electrocatalyst for oxygen reduction reaction in aluminum-air batteries

    NASA Astrophysics Data System (ADS)

    Xue, Yejian; Huang, Heran; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2017-08-01

    A novel La0.7Sr0.3MnO3-CeO2 (LSM-CeO2) hybrid catalyst for oxygen reduction reaction (ORR) has been synthesized by a facile one-pot method. The flower-like CeO2 with the diameter of about 3 μm is formed by the agglomeration of nanosheets with the thickness of about 40 nm. The LSM particles with the diameter of about 150 nm are well distributed on the flower-like CeO2, thus the interaction between LSM and CeO2 is built. Therefore, the LSM-CeO2 composite catalyst exhibits the much higher catalytic activity toward ORR with the direct four-electron transfer mechanism in alkaline solution than LSM or CeO2. Furthermore, the stability of LSM-CeO2 is superior to that of Pt/C, and the current retention is 93% after 100000 s. The maximum power density of the aluminum-air battery using LSM-CeO2 as the ORRC can reach 238 mW cm-2, which is about 29% higher than that with LSM (184 mW cm-2). It indicates that LSM-CeO2 composite material is a promising cathodic electrocatalyst for metal-air batteries.

  16. Surface Catalysis Modeling of Air-SiO2 Systems Under Hypersonic Conditions Using ReaxFF MD Simulation

    NASA Astrophysics Data System (ADS)

    Norman, Paul; Schwartzentruber, Tom; Cozmuta, Ioana

    2009-11-01

    The high-speed entry of a blunt body into Earth's atmosphere brings about the dissociation of diatomic nitrogen and oxygen molecules via the shockwave formed in front of the body. Through surface catalysis, these dissociated atoms can recombine on the heat shield of the body, increasing its overall heating. The goal of this project is to study surface catalysis on amorphous silicon-dioxide (SiO2), a significant component in the reusable thermal protection system used on the Space Shuttle. Specifically, our objective is to determine the rates of recombination of monatomic N and O for the range of temperatures and pressures experienced by a heat shield during Earth re-entry. Additionally, we aim to determine the rates of specific reaction mechanisms on a SiO2 surface, including adsorption, desorption, surface diffusion, and various recombination processes. This is accomplished by performing large reactive molecular dynamics simulations using the ReaxFF force field, which naturally allows bond formation/breaking to occur during the course of a molecular dynamics simulation. Several methods for speeding up the equilibration and collection of rates for low-pressure gas-surface systems (typical of re-entry conditions) where events become infrequent will also be discussed.

  17. Study on the Conductance and Photo-Conductance of ZnO Thin Films at Different Temperatures in Air and N2-Atmosphere

    NASA Astrophysics Data System (ADS)

    Burruel-Ibarra, S. E.; Cruz-Vázquez, C.; Bernal, R.; Aceves, R.; Orante-Barrón, V. R.; Grijalva-Monteverde, H.; Piters, T. M.; Castaño, V. M.

    2016-01-01

    We report the photoconductance of ZnO thin films obtained from thermally treated ZnS films grown by a chemical bath deposition method. The measurements of photo-conductance were performed in an atmosphere of air or nitrogen (N2) at different temperatures between 300 K and 375 K. The augmented conductance after ultraviolet (UV) irradiation (330-380 nm) in air fades away slowly to its original value, whereas in a nitrogen atmosphere, a significant part of the augmented conductance remains. Measurements of electrical conductance as a function of temperature in N2 or air, in the dark or the light, seem to indicate that the donor concentration is increased during the UV irradiation, suggesting that oxygen vacancies and interstitials are created. An alternative model for the photoconduction in ZnO is proposed in which the slow increase of conduction during irradiation is explained by an increase of donors instead of photoelectrons. In this model, the photoelectrons would only play a role in the mechanism of the creation of donors.

  18. Nonhomogeneous surface properties of parylene-C film etched by an atmospheric pressure He/O2 micro-plasma jet in ambient air

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Yang, Bin; Chen, Xiang; Wang, Xiaolin; Yang, Chunsheng; Liu, Jingquan

    2016-10-01

    Surface properties of parylene-C film etched by an atmospheric pressure He/O2 micro-plasma jet in ambient air were investigated. The morphologies and chemical compositions of the etched surface were analyzed by optical microscopy, SEM, EDS, XPS and ATR-FTIR. The microscopy and SEM images showed the etched surface was nonhomogeneous with six discernable ring patterns from the center to the outside domain, which were composed of (I) a central region; (II) an effective etching region, where almost all of the parylene-C film was removed by the plasma jet with only a little residual parylene-C being functionalized with carboxyl groups (Cdbnd O, Osbnd Cdbnd O-); (III) an inner etching boundary; (IV) a middle etching region, where the film surface was smooth and partially removed; (V) an outer etching boundary, where the surface was decorated with clusters of debris, and (VI) a pristine parylene-C film region. The analysis of the different morphologies and chemical compositions illustrated the different localized etching process in the distinct regions. Besides, the influence of O2 flow rate on the surface properties of the etched parylene-C film was also investigated. Higher volume of O2 tended to weaken the nonhomogeneous characteristics of the etched surface and improve the etched surface quality.

  19. Photocatalytic oxidation of methyl ethyl ketone over sol-gel and commercial TiO2 for the improvement of indoor air.

    PubMed

    Raillard, C; Héquet, V; Le Cloirec, P; Legrand, J

    2006-01-01

    This work focuses on the photocatalytic oxidation of gaseous methyl ethyl ketone chosen as a typical indoor air pollutant. Two types of TiO coatings were prepared and deposited on glass plates: one using the commercial Degussa P25 TiO2 and the other one by sol-gel method. The first objective of this study was to compare different ways of preparing thin films of sol-gel TiO2 coated on glass plates, taking into account their general aspect and their photocatalytic efficiency. Several parameters were tested, such as the stabilising agent, the glass type of the support, the number of coatings and the calcination temperature. One of the synthesised materials was then kept to carry out the following study. The study aimed to assess the influence of TiO2 coating types on the effect of water vapour. This was achieved by performing MEK photocatalytic degradation kinetics under two levels of humidity at a fixed temperature. Experimental results were then modelled by the Langmuir-Hinshelwood equation. The obtained parameters gave specific trends in function of the considered catalyst. The second part of this work was to identify MEK degradation byproducts during its photocatalytic oxidation. The main detected intermediate was acetaldehyde, followed by methyl formate. A MEK degradation pathway was then proposed.

  20. Bis(3,5-dimethyl-1H-pyrazole-κN 2)(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)copper(II)

    PubMed Central

    Lin, Yuan-Yuan; Yu, Yan-Ping; Liu, Bing-Xin; Zhang, Liang-Jun

    2009-01-01

    In the crystal structure of the title compound, [Cu(C7H3NO4)(C5H8N2)2], the CuII cation assumes a distorted trigonal–bipyramidal coordination geometry formed by a pyridine-2,6-dicarboxyl­ate dianion and two 3,5-dimethyl-1H-pyrazole mol­ecules. N—H⋯O hydrogen bonding is present in the crystal structure. PMID:21582065

  1. Flow-field differences and electromagnetic-field properties of air and N2 inductively coupled plasmas

    NASA Astrophysics Data System (ADS)

    Yu, Minghao; Yamada, Kazuhiko; Takahashi, Yusuke; Liu, Kai; Zhao, Tong

    2016-12-01

    A numerical model for simulating air and nitrogen inductively coupled plasmas (ICPs) was developed considering thermochemical nonequilibrium and the third-order electron transport properties. A modified far-field electromagnetic model was introduced and tightly coupled with the flow field equations to describe the Joule heating and inductive discharge phenomena. In total, 11 species and 49 chemical reactions of air, which include 5 species and 8 chemical reactions of nitrogen, were employed to model the chemical reaction process. The internal energy transfers among translational, vibrational, rotational, and electronic energy modes of chemical species were taken into account to study thermal nonequilibrium effects. The low-Reynolds number Abe-Kondoh-Nagano k-ɛ turbulence model was employed to consider the turbulent heat transfer. In this study, the fundamental characteristics of an ICP flow, such as the weak ionization, high temperature but low velocity in the torch, and wide area of the plasma plume, were reproduced by the developed numerical model. The flow field differences between the air and nitrogen ICP flows inside the 10-kW ICP wind tunnel were made clear. The interactions between the electromagnetic and flow fields were also revealed for an inductive discharge.

  2. Removal of NO2 and O3 generated from corona discharge in indoor air cleaning with MnO2 catalyst

    NASA Astrophysics Data System (ADS)

    Ge, H.; Yu, R.; Mi, D.; Zhu, Y. M.

    2013-03-01

    The production rules and removal efficiency of harmful byproducts such as NO2 and O3 generated from DC corona discharge in indoor air cleaning were investigated. The production behaviours of NO2 and O3 and the relationship between the amount of catalyst (MnO2) and the removal rate of harmful byproducts were experimentally studied. Further, indoor application tests were carried out in a closed room with 90 m3. The results showed that the concentrations of NO2 and O3 produced by corona discharge linearly increased with discharge time. The NO2 yield is larger than O3 by almost one order of magnitude under the same discharge power. To satisfy the demand of Standard of Indoor Air Quality (GB/T18883-2002), the power consumption of unit volume should be less than 1 W m-3 and the catalyst MnO2 consumptions in positive-negative corona discharge were 200 cm3 W-1 and 100 cm3 W-1, respectively.

  3. Air annealing effects on the optical properties of ZnO SnO2 thin films deposited by a filtered vacuum arc deposition system

    NASA Astrophysics Data System (ADS)

    Çetinörgü, E.; Goldsmith, S.; Boxman, R. L.

    2006-03-01

    ZnO-SnO2 transparent and conducting thin films were deposited on microscope glass substrates by a filtered vacuum arc deposition (FVAD) system. The cathode was prepared with 50%:50% atomic concentration of Zn:Sn. The films were annealed in air at 500 °C for 1 h. Structural and compositional analyses were obtained using XRD and XPS diagnostics. X-ray diffraction analysis indicated that as-deposited and air-annealed thin ZnO-SnO2 films were amorphous. The atomic ratio of Zn to Sn in the film obtained using the 50%:50% cathode as determined by XPS analysis was ~2.7:1 in the bulk film. The optical properties were determined from normal incidence transmission measurements. Film transmission in the visible was 70% to 90%, affected by interference effects. Annealed films did not show higher transmission in the VIS compared to as-deposited films. Assuming that the interband electron transition is direct, the optical band gap was found to be in the range 3.34-3.61 eV for both as-deposited and annealed films. However, the average Eg for annealed films was 3.6 eV, larger by 0.2 eV than that of as-deposited. The refractive index n increased while the extinction index k decreased significantly with annealing.

  4. Measurements of the CO_2 15 μm Band System Broadened by Air, N_2 and CO_2 at Terrestrial Atmospheric Temperatures

    NASA Astrophysics Data System (ADS)

    Smith, M. A. H.; Devi, V. Malathy; Benner, D. Chris; Blake, T. A.; Sams, R. L.

    2009-06-01

    In earth remote sensing, retrievals of atmospheric temperature profiles are often based on observed radiances in infrared spectral regions where emission from atmospheric CO_2 predominates. To achieve improved retrieval accuracy, systematic errors in the forward model must be reduced, especially those associated with errors in the spectroscopic line calculation. We have recorded more than 110 new high-resolution infrared spectra of the 15-μm band system of CO_2 to accurately determine line intensities, self-, air- and N_2-broadened widths and pressure-induced line shifts, along with their temperature dependences. The spectra were recorded with the Bruker IFS 120 HR Fourier transform spectrometer at Pacific Northwest National Laboratory (PNNL) and temperature-controlled sample cells. Sample temperatures were between 206K and 298K. Maximum total pressures were 15 Torr for self-broadening and 613 Torr for air- and N_2-broadening. Analysis is done using a multispectrum fitting technique to retrieve the spectroscopic parameters. Line mixing and other non-Lorentz, non-Voigt line shapes are also assessed. The resulting line parameters are compared with the HITRAN database and with other measurements. D. Chris Benner, C.P. Rinsland, V. Malathy Devi, M.A.H. Smith, and D. Atkins, J. Quant. Spectrosc. Radiat. Transfer 53, 705-721 (1995) L.S. Rothman et al., J. Quant. Spectrosc. Radiat. Transfer 96, 139-204 (2005) L.S. Rothman et al., J. Quant. Spectrosc. Radiat. Transfer, in press (2009)

  5. Heat-transfer distributions on biconics at incidence in hypersonic-hypervelocity He, N2, air, and CO2 flows

    NASA Technical Reports Server (NTRS)

    Miller, C. G.; Micol, J. R.; Gnoffo, P. A.; Wilder, S. E.

    1983-01-01

    Laminar heat transfer rates were measured on spherically blunted, 13 deg/7 deg on axis and bent biconics (fore cone bent 7 deg upward relative to aft cone) at hypersonic hypervelocity flow conditions in the Langley Expansion Tube. Freestream velocities from 4.5 to 6.9 km/sec and Mach numbers from 6 to 9 were generated using helium, nitrogen, air, and carbon dioxide test gases, resulting in normal shock density ratios from 4 to 19. Angle of attack, referenced to the axis of the aft cone, was varied from 0 to 20 deg in 4 deg increments. The effect of nose bend, angle of attack, and real gas phenomena on heating distributions are presented along with comparisons of measurement to prediction from a code which solves the three dimensional parabolized Navier-Stokes equations.

  6. 193Ir Mössbauer spectroscopy of Pt-IrO 2 nanoparticle catalysts developed for detection and removal of carbon monoxide from air

    NASA Astrophysics Data System (ADS)

    Sawicki, J. A.; Marcinkowska, K.; Wagner, F. E.

    2010-08-01

    Mössbauer spectroscopy of 73.0 keV gamma-ray transition in 193Ir and supplementary analytical techniques were used to study the microstructure and chemical form of polymer-supported hydrophobic bimetallic Pt-Ir catalysts for detection and removal of CO from humid air at ambient conditions. The catalysts, typically with a composition of 9 wt.% Pt and 1 wt.% Ir, were prepared by incipient wetness impregnation of polystyrene-divinylbenzene (SDB) granules with ethanol solutions of hexachloroplatinic and hexachloroiridic acids. This procedure, followed by reduction in H 2 or CO at only 200 °C or 250 °C, resulted in formation of highly-dispersed Pt-Ir particles usually smaller than 20 nm and having high catalytic activity and selectivity. Mössbauer spectra of 73.0 keV gamma-ray transition in 193Ir were taken after consecutive steps of preparation and exposure of catalysts to better understand and further improve the fabrication processes. In the as-impregnated state, iridium was found mostly as Ir(III) in [IrCl 6] 3- ions, with only a small fraction of Ir(IV) in [IrCl 6] 2- ions. The iridium in bimetallic clusters formed by reduction in hydrogen showed a strong tendency towards oxidation on exposure to air at room temperature, while Pt remained mostly metallic. In the most active and stable catalysts, the Ir and Pt in metallic regions of the clusters did not tend to segregate, unlike in Pt-Ir/silica-supported catalysts studied by us earlier. Further, this study shows that the IrO 2-like regions in the clusters exhibit stronger deviations from local symmetry and stoichiometry of crystalline IrO 2 than observed previously in Pt-Ir/silica catalysts. Our study also indicates that in the examined Pt-IrO 2 nanoparticles iridium largely provides the dissociative O 2 adsorption sites, while the CO adsorption occurs primarily at metallic Pt sites.

  7. Fundamental understanding of the thermal degradation mechanisms of waste tires and their air pollutant generation in a N2 atmosphere.

    PubMed

    Kwon, Eilhann; Castaldi, Marco J

    2009-08-01

    The thermal decomposition of waste tires has been characterized via thermo-gravimetric analysis (TGA) tests, and significant mass loss has been observed between 300 and 500 degrees C. A series of gas chromatography-mass spectrometer (GC-MS) measurements, in which the instrument was coupled to a TGA unit, have been carried out to investigate the thermal degradation mechanisms as well as the air pollutant generation including volatile organic carbons (VOCs) and polycyclic aromatic hydrocarbons (PAHs) in a nitrogen atmosphere. In order to understand fundamental information on the thermal degradation mechanisms of waste tires, the main constituents of tires, poly-isoprene rubber (IR) and styrene butadiene rubber (SBR), have been studied under the same conditions. All of the experimental work indicated that the bond scission on each monomer of the main constituents of tires was followed by hydrogenation and gas phase reactions. This helped to clarify the independent pathways and species attributable to IR and SBR during the pyrolysis process. To extend that understanding to a more practical level, a flow-through reactor was used to test waste tire, SBR and IR samples in the temperature range of 500-800 degrees C at a heating rate of approximately 200 degrees C. Lastly, the formation of VOCs (approximately 1-50 PPMV/10 mg of sample) and PAHs (approximately 0.2-7 PPMV/10 mg of sample) was observed at relatively low temperatures compared to conventional fuels, and its quantified concentration was significantly high due to the chemical structure of SBR and IR. The measurement of chemicals released during pyrolysis suggests not only a methodology for reducing the air pollutants but also the feasibility of petrochemical recovery during thermal treatment.

  8. Effect of MnO2 layers on transport properties of Lan-nxCa1+nxMnn-yCryO3n+1 (n=2, 3; x=0.3; y=0.075, 0.15, 0.3)

    NASA Astrophysics Data System (ADS)

    Khan, M. N. I.; Basith, M. A.; Huq, M.; Mollah, S.

    2007-12-01

    A series of bulk polycrystalline layered perovskite manganites Lan-nxCa1+nxMnn-yCryO3n+1 (n=2, 3; x=0.3; y=0.075, 0.15, 0.3) are prepared by conventional solid-state reaction technique and the effect of MnO2 layers on their transport properties are studied. Powder X-ray diffraction (XRD) patterns of the samples indicate their single-phase character. Metal insulator (MI) transition is observed in both Cr-doped and undoped samples. There is a systematic change of MI transition temperature with the increase of Cr concentration. Results on the transport properties of these samples have indicated methodical variations in a number of features like electrical resistivity, MI transition, low-field magnetoresistance, etc. with the number of MnO2 layers. A regular variation of different features is also observed when Mn site is substituted by Cr.

  9. The Effect of O2, H2O, and N2 on the Fatigue Crack Growth Behavior of an Alpha + Beta Titanium Alloy at 24 C and 177 C

    NASA Technical Reports Server (NTRS)

    Smith, Stephen W.; Piascik, Robert S.

    2001-01-01

    To study the effects of atmospheric species on the fatigue crack growth behavior of an a+B titanium alloy (Ti 6-2-2-2-2) at room temperature and 177 C, fatigue tests were performed in laboratory air, ultrahigh vacuum, and high purity water vapor, oxygen, nitrogen and helium at various partial pressures. Accelerated fatigue crack growth rates in laboratory air compared to ultrahigh vacuum are linked to the damaging effects of both water vapor and oxygen. Observations of the fatigue crack growth behavior in ultrahigh purity environments, along with surface film analysis using X-ray photoelectron spectroscopy (XPS), suggest that multiple crack-tip processes govern the damaging effects of air. Three possible mechanisms are proposed: 1) at low pressure (less than 10(exp -1) Pa), accelerated da/dN is likely due to monolayer adsorption on crack-tip surfaces presumably resulting in decreased bond strengths at the fatigue crack tip, 2) for pressures greater than 10(exp -1) Pa, accelerated da/dN in oxygen may result from oxidation at the crack tip limiting reversible slip, and 3) in water vapor, absorption of atomic hydrogen at the reactive crack tip resulting in process zone embrittlement.

  10. Influence of Enhanced O2 Provision on the Discharge Performance of Li-air Batteries by Incorporating Fluoroether.

    PubMed

    Wan, Hao; Mao, Ya; Liu, Zixuan; Bai, Qingyou; Peng, Zhe; Bao, Jingjing; Wu, Gang; Liu, Yang; Wang, Deyu; Xie, Jingying

    2017-04-10

    As the first step during discharge, the mass transfer of oxygen should play a crucial role in Li-air batteries to tailor the growth of discharge products, however, not enough attention has been paid to this issue. Herein, we introduce an oxygen-enriching cosolvent, 1,2-(1,1,2,2-tetrafluoroethoxy) ethane (FE1), into the electrolyte, and investigate its influence on the discharge performance. The incorporation of this novel cosolvent consistently enhances the oxygen solubility of the electrolyte, and improves the oxygen diffusivity following a volcano-shape trend peaking at 50 % FE1. It is interesting that the discharge capacities obtained with the investigated electrolytes share the similar volcano trends as the oxygen transport under 50 mA gcarbon(-1) and higher current densities. The improved oxygen diffusion could benefit the volumetric utilization of the air cathode, especially at the separator side, probably owing to the fast oxygen transport to moderate its concentration gradient. Our results demonstrate the importance of oxygen provision, which easily becomes the capacity-determining factor. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Electrical Behavior of SnO2 Polycrystalline Ceramic Pieces Formed by Slip Casting: Effect of Surrounding Atmosphere (Air and CO)

    NASA Astrophysics Data System (ADS)

    Aguilar-Paz, C. J.; Ochoa-Muñoz, Y.; Ponce, M. A.; Rodríguez-Páez, J. E.

    2016-01-01

    Pieces of porous polycrystalline SnO2 with and without cobalt have been formed by the slip-casting method, using ceramic powders synthesized by the controlled precipitation method. A suitable methodology was developed for forming and sintering the pieces to enable controlled modification of their microstructure, principally grain size, porosity, and type of intergranular contacts. Better control of the microstructure was obtained in the samples containing cobalt. In these, predominance of open necks and intergranular contacts was observed, which can represent Schottky barriers. Because of its good structural homogeneity, porosity, and small grain size (of the order of 1 μm), the sample with 2 mol.% Co sintered at 1250°C for 2 h was selected for electrical characterization by complex impedance spectroscopy, varying the operating temperature, concentration and nature of the surrounding gas (air or CO), and bias voltage. The resulting R p and C p curves were very sensitive to variation in these parameters, being most obvious for the C p curves, which showed a phenomenon of low-frequency dispersion when bias voltages other than zero were used, in the presence of O2, and at operating temperature of 280°C. The electrical behavior of the SnO2 with 2 mol.% Co sample sintered at 1250°C was consistent with the nature and microstructural characteristics of the active material and was justified based on the presence of shallow- and deep-type defects, and variations in barrier height and width, caused by adsorption of gas molecules.

  12. Air purification equipment combining a filter coated by silver nanoparticles with a nano-TiO2 photocatalyst for use in hospitals

    NASA Astrophysics Data System (ADS)

    Son Le, Thanh; Hien Dao, Trong; Nguyen, Dinh Cuong; Chau Nguyen, Hoai; Balikhin, I. L.

    2015-03-01

    X-ray diffraction, scanning electron microscopy and transmission electron microscopy showed that TiO2 particles synthesized by a sol-gel procedure exhibited uniform size about 16-20 nm. This nanopowder was deposited on a porous quartz tube (D = 74 mm, L = 418 mm, deposit density ˜16.4 mg cm-2) through an intermediate adhesive polymethylmethacrylate layer to manufacture a photocatalytic filter tube. A polypropylene pre-filter was coated with a nanosilver layer (particle size ˜20 nm) prepared by aqueous molecular solution method. An air cleaner of 250 m3 h-1 capacity equipped with this pre-filter, an electrostatic air filter, 4 photocatalytic filter tubes and 4 UV-A lamps (36 W) presented the high degradation ability for certain volatile organic compounds (VOCs), bacteria and fungi. The VOCs degradation performances of the equipment with respect to divers compounds are different: in a 10 m3 box, 91.6% of butanol was removed within 55 min, 80% of acetone within 100 min, 70.1% of diethyl ether within 120 min and only 43% of benzene was oxidized within 150 min. Over 99% of bacteria and fungi were killed after the air passage through the equipment. For application, it was placed in the intensive care room (volume of 125 m3) of E hospital in Hanoi; 69% of bacteria and 63% of fungi were killed within 6 h.

  13. Method for measuring temperatures and densities in hypersonic wind tunnel air flows using laser-induced O(2) fluorescence.

    PubMed

    Laufer, G; McKenzie, R L; Fletcher, D G

    1990-11-20

    Laser-induced fluorescence in oxygen, in combination with Raman scattering, is shown to be an accurate means by which temperature, density, and their fluctuations owing to turbulence can be measured in air flows associated with high speed wind tunnels. For temperatures above 60 K and densities above 0.01 amagat, the uncertainties in the temperature and density measurements can be <2%, if the signal uncertainties are dominated by photon statistical noise. The measurements are unaffected by collisional quenching and can be achieved with laser fluences for which nonlinear effects are insignificant. Temperature measurements using laser-induced fluorescence alone have been demonstrated at known densities in the range of low temperatures and densities which are expected in a hypersonic wind tunnel.

  14. Graphene supported heterogeneous catalysts for Li-O2 batteries

    NASA Astrophysics Data System (ADS)

    Alaf, M.; Tocoglu, U.; Kartal, M.; Akbulut, H.

    2016-09-01

    In this study production and characterization of free-standing and flexible (i) graphene, (ii) α-MnO2/graphene, (iii) Pt/graphene (iv) α-MnO2/Pt/graphene composite cathodes for Li-air batteries were reported. Graphene supported heterogeneous catalysts were produced by a facile method. In order to prevent aggregation of graphene sheets and increase not only interlayer distance but also surface area, a trace amount multi-wall carbon nano tube (MWCNT) was introduced to the composite structure. The obtained composite catalysts were characterized by SEM, X-ray diffraction, N2 adsorption-desorption analyze and Raman spectroscopy. The electrochemical characterization tests including galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS) measurement of catalyst were carried out by using an ECC-Air test cell. These highly active graphene supported heterogeneous composite catalysts provide competitive properties relative to other catalyst materials for Li-air batteries.

  15. Removal of organic dye by air and macroporous ZnO/MoO3/SiO2 hybrid under room conditions

    NASA Astrophysics Data System (ADS)

    Yuan, Mengjia; Wang, Shengtian; Wang, Xiaohong; Zhao, Lingling; Hao, Tianhong

    2011-07-01

    A new macroporous ZnO/MoO3/SiO2 hybrid was synthesized by a method involving sol-gel technology and biomimetic synthesis. It was characterized by Elemental analysis, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) and scanning electron microscopy (SEM). Chemical degradation of 0.3 g/L Safranin T (ST) by air oxidation over macroporous ZnO/MoO3/SiO2 hybrid was studied. It was found that the decolorization efficiency and the chemical oxygen demand (COD) removal of ST reached above 95.3% and 93.2%, respectively, within 25 min at room temperature and atmospheric pressure. And the organic pollutant was mineralized to simple inorganic species such as HCO3-, Cl- and NO3-, while the total organic carbon (TOC) decreased 95.4%. The structure and morphology of the catalyst were still stable after six cycling runs and the leaching test showed negligible leaching effect.

  16. Self-terminated etching of GaN with a high selectivity over AlGaN under inductively coupled Cl2/N2/O2 plasma with a low-energy ion bombardment

    NASA Astrophysics Data System (ADS)

    Zhong, Yaozong; Zhou, Yu; Gao, Hongwei; Dai, Shujun; He, Junlei; Feng, Meixin; Sun, Qian; Zhang, Jijun; Zhao, Yanfei; DingSun, An; Yang, Hui

    2017-10-01

    Etching of GaN/AlGaN heterostructure by O-containing inductively coupled Cl2/N2 plasma with a low-energy ion bombardment can be self-terminated at the surface of the AlGaN layer. The estimated etching rates of GaN and AlGaN were 42 and 0.6 nm/min, respectively, giving a selective etching ratio of 70:1. To study the mechanism of the etching self-termination, detailed characterization and analyses were carried out, including X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS). It was found that in the presence of oxygen, the top surface of the AlGaN layer was converted into a thin film of (Al,Ga)Ox with a high bonding energy, which effectively prevented the underlying atoms from a further etching, resulting in a nearly self-terminated etching. This technique enables a uniform and reproducible fabrication process for enhancement-mode high electron mobility transistors with a p-GaN gate.

  17. Photochemistry of the indoor air pollutant acetone on Degussa P25 TiO2 studied by chemical ionization mass spectrometry.

    PubMed

    Schmidt, Catherine M; Buchbinder, Avram M; Weitz, Eric; Geiger, Franz M

    2007-12-20

    We have used chemical ionization mass spectrometry (CIMS) to study the adsorption and photochemistry of several oxygenated organic species adsorbed to Degussa P25 TiO2, an inexpensive catalyst that can be used to mineralize volatile organic compounds. The molecules examined in this work include the common indoor air pollutant acetone and several of its homologs and possible oxidation and condensation products that may be formed during the adsorption and/or photocatalytic degradation of acetone on titanium dioxide catalysts. We report nonreactive uptake coefficients for acetone, formic acid, acetic acid, mesityl oxide, and diacetone alcohol, and results from photochemical studies that quantify, on a per-molecule basis, the room-temperature photocatalytic conversion of the species under investigation to CO2 and related oxidation products. The data presented here imply that catalytic surfaces that enhance formate and acetate production from acetone precursors will facilitate the photocatalytic remediation of acetone in indoor environments, even at room temperature.

  18. Development of a Thermal Transport Database for Air Plasma Sprayed ZrO2 ? Y2O3 Thermal Barrier Coatings

    SciTech Connect

    Wang, Hsin; Dinwiddie, Ralph Barton; Porter, Wallace D

    2010-01-01

    Thermal Diffusivities of Air Plasma Sprayed (APS) thermal barrier coatings (TBCs) are measured by the laser flash method. The data are used to calculate thermal conductivity of TBCs when provided with density and specific heat data. Due to the complicated microstructure and other processing related parameters, thermal diffusivity of TBCs can vary as much as three to four fold. Data collected from over 200 free-standing ZrO2 7-8 wt%Y2O3 TBCs are presented. The large database gives a clear picture of the expected band of thermal diffusivity values. When this band is used as reference for thermal diffusivity of a specific TBC, the thermal transport property of TBC can be more precisely described. The database is intended to serve researchers and manufacturers of TBCs as a valuable source for evaluating their coatings.

  19. A Study of a QCM Sensor Based on TiO2 Nanostructures for the Detection of NO2 and Explosives Vapours in Air

    PubMed Central

    Procek, Marcin; Stolarczyk, Agnieszka; Pustelny, Tadeusz; Maciak, Erwin

    2015-01-01

    The paper deals with investigations concerning the construction of sensors based on a quartz crystal microbalance (QCM) containing a TiO2 nanostructures sensor layer. A chemical method of synthesizing these nanostructures is presented. The prepared prototype of the QCM sensing system, as well as the results of tests for detecting low NO2 concentrations in an atmosphere of synthetic air have been described. The constructed NO2 sensors operate at room temperature, which is a great advantage, because resistance sensors based on wide gap semiconductors often require much higher operation temperatures, sometimes as high as 500 °C. The sensors constructed by the authors can be used, among other applications, in medical and chemical diagnostics, and also for the purpose of detecting explosive vapours. Reactions of the sensor to nitroglycerine vapours are presented as an example of its application. The influence of humidity on the operation of the sensor was studied. PMID:25912352

  20. Epitaxial growth of thin films of rutile (TiO 2) on {100} surfaces of rutile single crystals reacted with Ga 2O 3 in air

    NASA Astrophysics Data System (ADS)

    Iguchi, E.; Tilley, R. J. D.

    1982-08-01

    Epitaxial films of rutile (TiO 2) were found to form on the {100} surface of rutile single crystals heated on Ga 2O 3 pellets in air at temperatures from 1373 to 1573 K. The nucleation and growth of the new oxide layer were observed by optical microscopy. The incubation period for the nucleation of the new layer, t0, was found to be t0=5.81×10 -5 exp[(163±41)/ RT](h), and the rate of th growth of the new layer, {dl }/{dt }, as {dl }/{dt }=1.48×10 5exp[-(196±14)/RT] ( mm/h) . The activation energies of these processes are 163 and 196 kJ mol -1, respectively. The kinetics for the nucleation and growth of the layers are discussed in terms of a vapour-solid reaction between a volatile gallium oxide species and the rutile crystal.

  1. Increased cardiac output, not pulmonary artery systolic pressure, increases intrapulmonary shunt in healthy humans breathing room air and 40% O2

    PubMed Central

    Elliott, Jonathan E; Duke, Joseph W; Hawn, Jerold A; Halliwill, John R; Lovering, Andrew T

    2014-01-01

    Blood flow through intrapulmonary arteriovenous anastomoses (IPAVAs) has been demonstrated to increase in healthy humans during a variety of conditions; however, whether or not this blood flow represents a source of venous admixture (/) that impairs pulmonary gas exchange efficiency (i.e. increases the alveolar-to-arterial difference (A–aDO2)) remains controversial and unknown. We hypothesized that blood flow through IPAVAs does provide a source of /. To test this, blood flow through IPAVAs was increased in healthy humans at rest breathing room air and 40% O2: (1) during intravenous adrenaline (epinephrine) infusion at 320 ng kg−1 min−1 (320 ADR), and (2) with vagal blockade (2 mg atropine), before and during intravenous adrenaline infusion at 80 ng kg−1 min−1 (ATR + 80 ADR). When breathing room air the A–aDO2 increased by 6 ± 2 mmHg during 320 ADR and by 5 ± 2 mmHg during ATR + 80 ADR, and the change in calculated / was +2% in both conditions. When breathing 40% O2, which minimizes contributions from diffusion limitation and alveolar ventilation-to-perfusion inequality, the A–aDO2 increased by 12 ± 7 mmHg during 320 ADR, and by 9 ± 6 mmHg during ATR + 80 ADR, and the change in calculated / was +2% in both conditions. During 320 ADR cardiac output () and pulmonary artery systolic pressure (PASP) were significantly increased; however, during ATR + 80 ADR only was significantly increased, yet blood flow through IPAVAs as detected with saline contrast echocardiography was not different between conditions. Accordingly, we suggest that blood flow through IPAVAs provides a source of intrapulmonary shunt, and is mediated primarily by increases in rather than PASP. PMID:25085889

  2. Line parameters including temperature dependences of self- and air-broadened line shapes of 12C16O2: 1.6-μm region

    NASA Astrophysics Data System (ADS)

    Devi, V. Malathy; Benner, D. Chris; Sung, Keeyoon; Brown, Linda R.; Crawford, Timothy J.; Miller, Charles E.; Drouin, Brian J.; Payne, Vivienne H.; Yu, Shanshan; Smith, Mary Ann H.; Mantz, Arlan W.; Gamache, Robert R.

    2016-07-01

    Pressure-broadened line shapes in the 30013←00001 (ν1+4 ν20 +ν3) band of 12C16O2 at 6228 cm-1 are reanalyzed using new spectra recorded with sample temperatures down to 170 K. High resolution, high signal-to-noise (S/N) laboratory measurements of line shapes (Lorentz air- and self-broadened half-width coefficients, pressure-shift coefficients and off-diagonal relaxation matrix element coefficients) as a function of gas sample temperatures for various pressures and volume mixing ratios are presented. The spectra were recorded using two different Fourier transform spectrometers (FTS): (1) the McMath-Pierce FTS located at the National Solar Observatory on Kitt Peak, Arizona (and reported in Devi et al., J Mol Spectrosc 2007;245:52-80) and, (2) the Bruker IFS-125HR FTS at the Jet Propulsion Laboratory in Pasadena, California. The 19 spectra taken at Kitt Peak were all recorded near room temperature while the 27 Bruker spectra were acquired both at room temperature and colder temperatures (170-296 K). Various spectral resolutions (0.004-0.011 cm-1), absorption path lengths (2.46-121 m) and CO2 samples (natural and 12C-enriched) were included in the dataset. To maximize the accuracies of the various retrieved line parameters, a multispectrum nonlinear least squares spectrum fitting software program was used to adjust the ro-vibrational constants (G,B,D etc.) and intensity parameters (including Herman-Wallis terms) instead of directly measuring the individual line positions and intensities. To minimize systematic residuals, line mixing (via off-diagonal relaxation matrix elements) and quadratic speed dependence parameters were included in the analysis. Contributions from other weakly absorbing bands: the 30013←00001 and 30012←00001 bands of 13C16O2, the 30013←00001 band of 12C16O18O, hot bands 31113←01101 and 32212←02201 of 12C16O2, as well as the 40013←10001 and the 40014←10002 bands of 12C16O2, present within the fitted interval were also measured

  3. A randomized pilot study comparing the role of PEEP, O2 flow, and high-flow air for weaning of ventilatory support in very low birth weight infants.

    PubMed

    Yang, Chang-Yo; Yang, Mei-Chin; Chu, Shih-Ming; Chiang, Ming-Chou; Lien, Reyin

    2017-09-06

    There is a lack of evidence to guide step-wise weaning of positive pressure respiratory support for premature infants. This study sought to compare the efficacy of three weaning protocols we designed to facilitate weaning of very low birth weight (VLBW, less than 1500 g) preterm infants from nasal continuous positive airway pressure (NCPAP) support. This was a prospective, randomized, controlled trial of VLBW preterm infants who received positive pressure ventilatory support in our neonatal intensive care unit (NICU) from April 2008 through March 2009. When these infants were weaned to CPAP as their last step of respiratory support, they would be randomly assigned to one of the following three groups as their further weaning methods (M): (M1) CPAP group, (M2) O2 flow group, and (M3) air flow group. The time period they needed to wean off any kind of respiratory support, as well as the likelihood of developing relevant prematurity related morbidities, were compared among patients using different weaning modalities. 181 patients were enrolled in the study. Their gestational age (GA) and birth weight (BW) were 29.1 ± 2.5, 28.7 ± 2.4, 28.7 ± 2.4 (mean ± SD) weeks and 1142 ± 232, 1099 ± 234, 1083 ± 219 g, in M1, M2 and M3, respectively. The time (period) needed to wean off support was 16.0 ± 10.0 days (M1), 11.6 ± 6.4 days (M2), and 15.0 ± 8.9 days (M3), respectively (p = .033). Incidence of retinopathy of prematurity (ROP) and bronchopulmonary dysplasia (BPD) were both significantly higher in the O2 flow group (p = .048). Although using low oxygen flow significantly shortens CPAP weaning time, it may increase risks of BPD and ROP, both known to be related to oxygen toxicity. Unless the infant has BPD and is O2-dependent, clinicians should consider using air flow or just splinting with no support at all when weaning NCPAP. Copyright © 2017. Published by Elsevier B.V.

  4. The use of different plasma gases (Ar, N(2) and air) for CMP-OES: figures of merit and temperature measurements.

    PubMed

    Bings, N H; Broekaert, J A

    1996-06-01

    A comparative study of a 600 W capacitively coupled microwave plasma (CMP) operated with different plasma gases (Ar, N(2) and air) with respect to the achieved detection limits for Fe, Cr, Zn, Ca and Mg have been carried out. Radially and axially resolved rotational temperatures (T(rot)), excitation temperatures (T(exc)) and electron number densities (n(e)) of these plasmas have been determined using OH (T(rot)), Fe (T(exc)) and Mg (n(e)) as thermometric species. The influence of different gas flow rates on T(rot), T(exc) and n(e), and of Li as an easily ionized element on T(exc) has been investigated.

  5. Volume properties and refraction of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids lysine, threonine, and oxyproline (C60(C6H13N2O2)2, C60(C4H8NO3)2, and C60(C5H9NO2)2) at 25°C

    NASA Astrophysics Data System (ADS)

    Semenov, K. N.; Ivanova, N. M.; Charykov, N. A.; Keskinov, V. A.; Kalacheva, S. S.; Duryagina, N. N.; Garamova, P. V.; Kulenova, N. A.; Nabieva, A.

    2017-02-01

    Concentration dependences of the density of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids are studied by pycnometry. Concentration dependences of the average molar volumes and partial volumes of components (H2O and corresponding bisadducts) are calculated for C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems at 25°C. Concentration dependences of the indices of refraction of C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems are determined at 25°C. The concentration dependences of specific refraction and molar refraction of bisadducts and aqueous solutions of them are calculated.

  6. Morphological, structural, and chemical effects in response of novel carbide derived carbon sensor to NH3, N2O, and air.

    PubMed

    Adu, Kofi W; Li, Qixiu; Desai, Sharvil C; Sidorov, Anton N; Sumanasekera, Gamini U; Lueking, Angela D

    2009-01-06

    The response of two carbide derived carbons (CDCs) films to NH(3), N(2)O, and room air is investigated by four probe resistance at room temperature and pressures up to 760 Torr. The two CDC films were synthesized at 600 (CDC-600) and 1000 degrees C (CDC-1000) to vary the carbon morphology from completely amorphous to more ordered, and determine the role of structure, surface area, and porosity on sensor response. Sensor response time followed kinetic diameter and indicated a more ordered carbon structure slowed response due to increased tortuosity caused by the formation of graphitic layers at the particle fringe. Steady state sensor response was greater for the less-ordered material, despite its decreased surface area, decreased micropore volume, and less favorable surface chemistry, suggesting carbon structure is a stronger predictor of sensor response than surface chemistry. The lack of correlation between adsorption of the probe gases and sensor response suggests chemical interaction (charge transfer) drive sensor response within the material; N(2)O response, in particular, did not follow simple adsorption behavior. Based on Raman and FTIR characterization, carbon morphology (disorder) appeared to be the determining factor in overall sensor response, likely due to increased charge transfer between gases and carbon defects of amorphous or disordered regions. The response of the amorphous CDC-600 film to NH(3) was 45% without prior oxidation, showing amorphous CDCs have promise as chemical sensors without additional pretreatment common to other carbon sensors.

  7. Influence of velocity effects on the shape of N2 (and air) broadened H2O lines revisited with classical molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Ngo, N. H.; Tran, H.; Gamache, R. R.; Bermejo, D.; Domenech, J.-L.

    2012-08-01

    The modeling of the shape of H2O lines perturbed by N2 (and air) using the Keilson-Storer (KS) kernel for collision-induced velocity changes is revisited with classical molecular dynamics simulations (CMDS). The latter have been performed for a large number of molecules starting from intermolecular-potential surfaces. Contrary to the assumption made in a previous study [H. Tran, D. Bermejo, J.-L. Domenech, P. Joubert, R. R. Gamache, and J.-M. Hartmann, J. Quant. Spectrosc. Radiat. Transf. 108, 126 (2007)], 10.1016/j.jqsrt.2007.03.009, the results of these CMDS show that the velocity-orientation and -modulus changes statistically occur at the same time scale. This validates the use of a single memory parameter in the Keilson-Storer kernel to describe both the velocity-orientation and -modulus changes. The CMDS results also show that velocity- and rotational state-changing collisions are statistically partially correlated. A partially correlated speed-dependent Keilson-Storer model has thus been used to describe the line-shape. For this, the velocity changes KS kernel parameters have been directly determined from CMDS, while the speed-dependent broadening and shifting coefficients have been calculated with a semi-classical approach. Comparisons between calculated spectra and measurements of several lines of H2O broadened by N2 (and air) in the ν3 and 2ν1 + ν2 + ν3 bands for a wide range of pressure show very satisfactory agreement. The evolution of non-Voigt effects from Doppler to collisional regimes is also presented and discussed.

  8. Influence of velocity effects on the shape of N2 (and air) broadened H2O lines revisited with classical molecular dynamics simulations.

    PubMed

    Ngo, N H; Tran, H; Gamache, R R; Bermejo, D; Domenech, J-L

    2012-08-14

    The modeling of the shape of H(2)O lines perturbed by N(2) (and air) using the Keilson-Storer (KS) kernel for collision-induced velocity changes is revisited with classical molecular dynamics simulations (CMDS). The latter have been performed for a large number of molecules starting from intermolecular-potential surfaces. Contrary to the assumption made in a previous study [H. Tran, D. Bermejo, J.-L. Domenech, P. Joubert, R. R. Gamache, and J.-M. Hartmann, J. Quant. Spectrosc. Radiat. Transf. 108, 126 (2007)], the results of these CMDS show that the velocity-orientation and -modulus changes statistically occur at the same time scale. This validates the use of a single memory parameter in the Keilson-Storer kernel to describe both the velocity-orientation and -modulus changes. The CMDS results also show that velocity- and rotational state-changing collisions are statistically partially correlated. A partially correlated speed-dependent Keilson-Storer model has thus been used to describe the line-shape. For this, the velocity changes KS kernel parameters have been directly determined from CMDS, while the speed-dependent broadening and shifting coefficients have been calculated with a semi-classical approach. Comparisons between calculated spectra and measurements of several lines of H(2)O broadened by N(2) (and air) in the ν(3) and 2ν(1) + ν(2) + ν(3) bands for a wide range of pressure show very satisfactory agreement. The evolution of non-Voigt effects from Doppler to collisional regimes is also presented and discussed.

  9. Nitrogen transfers and air-sea N2O fluxes in the upwelling off Namibia within the oxygen minimum zone: a 3-D model approach

    NASA Astrophysics Data System (ADS)

    Gutknecht, E.; Dadou, I.; Le Vu, B.; Cambon, G.; Sudre, J.; Garçon, V.; Machu, E.; Rixen, T.; Kock, A.; Flohr, A.; Paulmier, A.; Lavik, G.

    2011-04-01

    As regions of high primary production and being often associated to Oxygen Minimum Zones (OMZs), Eastern Boundary Upwelling Systems (EBUS) represent key regions for the oceanic nitrogen (N) cycle. Indeed, by exporting the Organic Matter (OM) and nutrients produced in the coastal region to the open ocean, EBUS can play an important role in sustaining primary production in subtropical gyres. Losses of fixed inorganic N, through denitrification and anammox processes and through nitrous oxide (N2O) emissions to the atmosphere, take place in oxygen depleted environments such as EBUS, and alleviate the role of these regions as a source of N. In the present study, we developed a 3-D coupled physical/biogeochemical (ROMS/BioBUS) model for investigating the full N budget in the Namibian sub-system of the Benguela Upwelling System (BUS). The different state variables of a climatological experiment have been compared to different data sets (satellite and in situ observations) and show that the model is able to represent this biogeochemical oceanic region. The N transfer is investigated in the Namibian upwelling system using this coupled model, especially in the Walvis Bay area between 22° S and 24° S where the OMZ is well developed (O2 < 0.5 ml O2 l-1). The upwelling process advects 24.2 × 1010 mol N yr-1 of nitrate enriched waters over the first 100 m over the slope and over the continental shelf. The meridional advection by the alongshore Benguela current brings also nutrient-rich waters with 21.1 × 1010 mol N yr-1. 10.5 × 1010 mol N yr-1 of OM are exported outside of the continental shelf (between 0 and 100-m depth). 32.4% and 18.1% of this OM are exported by advection in the form of Dissolved and Particulate Organic Matters (DOM and POM), respectively, however vertical sinking of POM represents the main contributor (49.5%) to OM export outside of the first 100-m depth of the water column on the continental shelf. The continental slope also represents a net N export

  10. Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature, pH, and air-flow.

    PubMed

    Al-Rasheed, Radwan; Cardin, David J

    2003-06-01

    We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO(2) (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 gl(-1); while the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure oxygen, an optimal flow rate was observed at 300 ml min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 (+/-0.6) kJ mol(-1).

  11. Air-gating and chemical-gating in transistors and sensing devices made from hollow TiO2 semiconductor nanotubes.

    PubMed

    Alivov, Yahya; Funke, Hans; Nagpal, Prashant

    2015-07-24

    Rapid miniaturization of electronic devices down to the nanoscale, according to Moore's law, has led to some undesirable effects like high leakage current in transistors, which can offset additional benefits from scaling down. Development of three-dimensional transistors, by spatial extension in the third dimension, has allowed higher contact area with a gate electrode and better control over conductivity in the semiconductor channel. However, these devices do not utilize the large surface area and interfaces for new electronic functionality. Here, we demonstrate air gating and chemical gating in hollow semiconductor nanotube devices and highlight the potential for development of novel transistors that can be modulated using channel bias, gate voltage, chemical composition, and concentration. Using chemical gating, we reversibly altered the conductivity of nanoscaled semiconductor nanotubes (10-500 nm TiO2 nanotubes) by six orders of magnitude, with a tunable rectification factor (ON/OFF ratio) ranging from 1-10(6). While demonstrated air- and chemical-gating speeds were slow here (∼seconds) due to the mechanical-evacuation rate and size of our chamber, the small nanoscale volume of these hollow semiconductors can enable much higher switching speeds, limited by the rate of adsorption/desorption of molecules at semiconductor interfaces. These chemical-gating effects are completely reversible, additive between different chemical compositions, and can enable semiconductor nanoelectronic devices for 'chemical transistors', 'chemical diodes', and very high-efficiency sensing applications.

  12. Discharge performance of solid-state oxygen shuttle metal-air battery using Ca-stabilized ZrO2 electrolyte.

    PubMed

    Inoishi, Atsushi; Kim, Hack-Ho; Sakai, Takaaki; Ju, Young-Wan; Ida, Shintaro; Ishihara, Tatsumi

    2015-04-13

    The effects of metal choice on the electrochemical performance of oxygen-shuttle metal-air batteries with Ca-stabilized ZrO2 (CSZ) as the electrolyte and various metals as the anodes were studied at 1073 K. The equilibrium oxygen partial pressure (P O 2) in the anode chamber was governed by the metal used in the anode chamber. A lower-P O 2 environment in the anode decreased the polarization resistance of the anode. The oxidation of oxide ions to oxygen in the anode is drastically enhanced by the n-type conduction generated in the CSZ electrolyte when it is exposed to a reducing atmosphere. A high discharge potential and high capacity can be achieved in an oxygen-shuttle battery with a Li or Mg anode because of the fast anode reaction compared to that of cells with a Zn, Fe, or Sn anode. However, only the mildly reducing metals (Zn, Si, Fe, and Sn) can potentially be used in rechargeable metal-air batteries because the transport number of the CSZ electrolyte must be unity during charge and discharge. Oxygen shuttle rechargeable batteries with Fe, and Sn electrodes are demonstrated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. A Pleistocene ice core record of atmospheric O2 concentrations

    NASA Astrophysics Data System (ADS)

    Stolper, D. A.; Bender, M. L.; Dreyfus, G. B.; Yan, Y.; Higgins, J. A.

    2016-09-01

    The history of atmospheric O2 partial pressures (PO2) is inextricably linked to the coevolution of life and Earth’s biogeochemical cycles. Reconstructions of past PO2 rely on models and proxies but often markedly disagree. We present a record of PO2 reconstructed using O2/N2 ratios from ancient air trapped in ice. This record indicates that PO2 declined by 7 per mil (0.7%) over the past 800,000 years, requiring that O2 sinks were ~2% larger than sources. This decline is consistent with changes in burial and weathering fluxes of organic carbon and pyrite driven by either Neogene cooling or increasing Pleistocene erosion rates. The 800,000-year record of steady average carbon dioxide partial pressures (PCO2) but declining PO2 provides distinctive evidence that a silicate weathering feedback stabilizes PCO2 on million-year time scales.

  14. Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers.

    PubMed

    Mizuse, Kenta; Fujii, Asuka

    2011-04-21

    Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.

  15. Uniform mixing of antiferromagnetism and high- Tc superconductivity in multilayer copper oxides Ba2Can-1CunO2nF2 (n=2,3,4) with apical fluorines: C63u-NMR/NQR and F19-NMR studies

    NASA Astrophysics Data System (ADS)

    Shimizu, S.; Sakaguchi, T.; Mukuda, H.; Kitaoka, Y.; Shirage, P. M.; Kodama, Y.; Iyo, A.

    2009-02-01

    We report C63u-NMR/NQR and F19-NMR studies on the multilayered high- Tc copper oxides Ba2Can-1CunO2nF2 with n=2,3,4 , where n is the number of CuO2 planes. It is revealed that bilayered Ba2CaCu2O4F2 is an underdoped superconductor with hole carriers, which are introduced into CuO2 planes by an unexpected deviation from the nominal content of apical fluorines. In a previous paper, we proposed a self-doping mechanism as the origin of carrier doping in n=3 and n=4 ; in the mechanism, electrons are transferred from the inner CuO2 plane (IP) to the outer one (OP). However, since it has been found that the bilayered compound is hole doped, we have re-examined the superconducting and magnetic properties in n=3 and n=4 by C63u-NMR/NQR and F19-NMR . The extensive NMR studies have confirmed that the apical-fluorine compounds are not self-doped but hole doped and that antiferromagnetism (AFM) and superconductivity (SC) coexist in a single CuO2 plane. In n=4 , the AFM ordering occurs at TN=80K well above Tc=55K , where the respective AFM moments are MAFM=0.11μB and 0.18μB at the OP and the IP. In n=3 , on the other hand, the underdoped single IP exhibits a spontaneous moment MAFM=0.12μB at low temperatures and a peak in the nuclear-spin-lattice relaxation rate 1/T1 of F19 at TN=23K much lower than Tc=76K . We note that the increase in the number of IPs from one to two results in the strengthening of the interlayer coupling; TN increases as the interlayer coupling becomes stronger, although the doping levels for both compounds are comparable. Consequently, we conclude that the uniform mixing of AFM and SC is a general property inherent to a single CuO2 plane in an underdoped regime for hole doping. This conclusion incorporates the angle-resolved photoemission spectroscopy results on the n=4 compound [Chen , Phys. Rev. Lett. 97, 236401 (2006)]; it was found that the two Fermi sheets of the IP and OP are observed and that the SC gap opens at the IP and OP below Tc=55K .

  16. [Regulation of geochemical activity of microorganisms in a petroleum reservoir by injection of H2O2 or water-air mixture].

    PubMed

    Nazina, T N; Pavlova, N K; Ni, F; Shestakova, N M; Ivoĭlov, V S; Feng, Q; Dongyun, Z; Prusakova, T S; Beliaev, S S; Ivanov, M V

    2008-01-01

    In the course of pilot trials of biotechnologies for the enhancement of oil recovery in the Gangxi bed of the Dagang oil field (China), microbiological processes were investigated. The biotechnologies were based on injection into the petroleum reservoir of different oxygen sources (H2O2 solution or a water-air mixture) with nitrogen and phosphorus salts. The injection of water-air mixture with nitrogen and phosphorus salts resulted in an increase in the number of aerobic and anaerobic organotrophic bacteria, rates of sulfate reduction and methanogenesis in formation water and also the content of CO2 (from 4.8-12 to 15-23.2%) and methane (from 86-88 to 91.8%) in the gas. The preferential consumption of isotopically light bicarbonate by methanogens resulted in a higher content of the light 12C in methane; the delta13C/CH4 value changed from -45.1...-48.3 to -50.7...-59.3 per thousand). At the same time, mineral carbonates of the formation water became isotopically heavier; the delta13C/Sigmacarbonates value increased from 3.4...4.0 to 5.4...9.6 per thousand. Growth of hydrocarbon-oxidizing bacteria was accompanied by production of biosurfactants and decreased interfacial tension of formation water. Injection of H2O2 solution resulted in the activation of aerobic processes and in suppression of both sulfate reduction and methanogenesis. Methane content in the gas decreased from 86-88 to 75.4-79.8%, probably due to its consumption by methanotrophs. Due to consumption of isotopically light methane, the residual methane carbon became heavier, with the delta13C/CH4 values from -39.0 to -44.3 per thousand. At the same time, mineral carbonates of the formation water became isotopically considerably lighter; the delta13C/Sigmacarbonates value decreased from 5.4... 9.6 to -1.4...2.7 per thousand). The additional amount of oil recovered during the trial of both variants of biotechnological treatment was 3819 t.

  17. Atomic Layer Deposition of TiO2 for a High-Efficiency Hole-Blocking Layer in Hole-Conductor-Free Perovskite Solar Cells Processed in Ambient Air.

    PubMed

    Hu, Hang; Dong, Binghai; Hu, Huating; Chen, Fengxiang; Kong, Mengqin; Zhang, Qiuping; Luo, Tianyue; Zhao, Li; Guo, Zhiguang; Li, Jing; Xu, Zuxun; Wang, Shimin; Eder, Dominik; Wan, Li

    2016-07-20

    In this study we design and construct high-efficiency, low-cost, highly stable, hole-conductor-free, solid-state perovskite solar cells, with TiO2 as the electron transport layer (ETL) and carbon as the hole collection layer, in ambient air. First, uniform, pinhole-free TiO2 films of various thicknesses were deposited on fluorine-doped tin oxide (FTO) electrodes by atomic layer deposition (ALD) technology. Based on these TiO2 films, a series of hole-conductor-free perovskite solar cells (PSCs) with carbon as the counter electrode were fabricated in ambient air, and the effect of thickness of TiO2 compact film on the device performance was investigated in detail. It was found that the performance of PSCs depends on the thickness of the compact layer due to the difference in surface roughness, transmittance, charge transport resistance, electron-hole recombination rate, and the charge lifetime. The best-performance devices based on optimized TiO2 compact film (by 2000 cycles ALD) can achieve power conversion efficiencies (PCEs) of as high as 7.82%. Furthermore, they can maintain over 96% of their initial PCE after 651 h (about 1 month) storage in ambient air, thus exhibiting excellent long-term stability.

  18. Interaction of the indoor air pollutant acetone with Degussa P25 TiO2 studied by chemical ionization mass spectrometry.

    PubMed

    Schmidt, Catherine M; Weitz, Eric; Geiger, Franz M

    2006-11-07

    Preventing a build-up of indoor pollutant concentrations has emerged as a major goal in environmental chemistry. Here, we have applied chemical ionization mass spectrometry to study the interaction of acetone, a common indoor air pollutant, with Degussa P25 TiO2, an inexpensive catalyst that is widely used for the degradation of volatile organic compounds into CO2 and water. To better understand the adsorption of acetone onto Degussa P25, the necessary first step for its degradation, the experiments were carried out at room temperature in the absence of UV light. This allowed for the deconvolution of the nonreactive and reactive thermal binding processes on Degussa P25 at acetone partial pressures (10(-7)-10(-4) Torr) commonly found in indoor environments. On average, 30% of the adsorbed acetone is bound irreversibly, resulting in a surface coverage of irreversibly bound acetone of approximately 1 x 10(12) molecules/cm2 at 3-4 x 10(-5) Torr. Equilibrium and dynamic experiments yield a sticking coefficient of approximately 1 x 10(-4) that is independent of the acetone partial pressures examined here. Equilibrium binding constants and free energies of adsorption are reported.

  19. Binder-Free and Carbon-Free 3D Porous Air Electrode for Li-O2 Batteries with High Efficiency, High Capacity, and Long Life.

    PubMed

    Luo, Wen-Bin; Gao, Xuan-Wen; Shi, Dong-Qi; Chou, Shu-Lei; Wang, Jia-Zhao; Liu, Hua-Kun

    2016-06-01

    Pt-Gd alloy polycrystalline thin film is deposited on 3D nickel foam by pulsed laser deposition method serving as a whole binder/carbon-free air electrode, showing great catalytic activity enhancement as an efficient bifunctional catalyst for the oxygen reduction and evolution reactions in lithium oxygen batteries. The porous structure can facilitate rapid O2 and electrolyte diffusion, as well as forming a continuous conductive network throughout the whole energy conversion process. It shows a favorable cycle performance in the full discharge/charge model, owing to the high catalytic activity of the Pt-Gd alloy composite and 3D porous nickel foam structure. Specially, excellent cycling performance under capacity limited mode is also demonstrated, in which the terminal discharge voltage is higher than 2.5 V and the terminal charge voltage is lower than 3.7 V after 100 cycles at a current density of 0.1 mA cm(-2) . Therefore, this electrocatalyst is a promising bifunctional electrocatalyst for lithium oxygen batteries and this depositing high-efficient electrocatalyst on porous substrate with polycrystalline thin film by pulsed laser deposition is also a promising technique in the future lithium oxygen batteries research.

  20. Insights on the High-Temperature Operational Limits of ZrO2-Y2O3 TBCs Manufactured via Air Plasma Spray

    NASA Astrophysics Data System (ADS)

    Lima, Rogerio S.; Marple, Basil R.

    2017-02-01

    The effective high-temperature operation limit of a ZrO2-7-8 wt.%Y2O3 (YSZ) thermal barrier coating (TBC) manufactured via air plasma spray (APS) is considered to be 1300 °C. This is related to the metastable tetragonal t'-phase formed during the rapid quenching of the YSZ particles during spraying. The t'-phase transforms into the equilibrium tetragonal and cubic phases at temperatures ≥ 1300 °C, which can lead to the formation of the monoclinic phase of YSZ upon cooling to room temperature. This formation of the monoclinic phase is accompanied by a volume expansion that leads to TBC failure due to extensive micro-cracking. To further investigate this limitation, an APS YSZ TBC was sprayed on a CMSX-4 substrate. By using a thermal (laser) gradient cyclic testing, a temperature gradient was generated across the TBC/substrate system. The YSZ T-front and substrate backside T-back temperature levels were 1500 and 1000 °C, respectively. In cycle conditions (5-min or 1-h hot and 2-min cool), no TBC failure has been observed. This behavior was partially attributed to the unexpected absence of the monoclinic phase of the YSZ in the cycled coatings. Although preliminary, these results are promising regarding increasing the effective high-temperature operational limits of APS YSZ TBCs.

  1. Insights on the High-Temperature Operational Limits of ZrO2-Y2O3 TBCs Manufactured via Air Plasma Spray

    NASA Astrophysics Data System (ADS)

    Lima, Rogerio S.; Marple, Basil R.

    2017-03-01

    The effective high-temperature operation limit of a ZrO2-7-8 wt.%Y2O3 (YSZ) thermal barrier coating (TBC) manufactured via air plasma spray (APS) is considered to be 1300 °C. This is related to the metastable tetragonal t'-phase formed during the rapid quenching of the YSZ particles during spraying. The t'-phase transforms into the equilibrium tetragonal and cubic phases at temperatures ≥ 1300 °C, which can lead to the formation of the monoclinic phase of YSZ upon cooling to room temperature. This formation of the monoclinic phase is accompanied by a volume expansion that leads to TBC failure due to extensive micro-cracking. To further investigate this limitation, an APS YSZ TBC was sprayed on a CMSX-4 substrate. By using a thermal (laser) gradient cyclic testing, a temperature gradient was generated across the TBC/substrate system. The YSZ T- front and substrate backside T- back temperature levels were 1500 and 1000 °C, respectively. In cycle conditions (5-min or 1-h hot and 2-min cool), no TBC failure has been observed. This behavior was partially attributed to the unexpected absence of the monoclinic phase of the YSZ in the cycled coatings. Although preliminary, these results are promising regarding increasing the effective high-temperature operational limits of APS YSZ TBCs.

  2. Dissociative recombination of O2(+), NO(+) and N2(+)

    NASA Technical Reports Server (NTRS)

    Guberman, S. L.

    1983-01-01

    A new L(2) approach for the calculation of the threshold molecular capture width needed for the determination of DR cross sections was developed. The widths are calculated with Fermi's golden rule by substituting Rydberg orbitals for the free electron continuum coulomb orbital. It is shown that the calculated width converges exponentially as the effective principal quantum number of the Rydberg orbital increases. The threshold capture width is then easily obtained. Since atmospheric recombination involves very low energy electrons, the threshold capture widths are essential to the calculation of DR cross sections for the atmospheric species studied here. The approach described makes use of bound state computer codes already in use. A program that collects width matrix elements over CI wavefunctions for the initial and final states is described.

  3. Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery.

    PubMed

    Xu, Nengneng; Liu, Yuyu; Zhang, Xia; Li, Xuemei; Li, Aijun; Qiao, Jinli; Zhang, Jiujun

    2016-09-20

    α-MnO2 nanotubes-supported Co3O4 (Co3O4/MnO2) and its carbon nanotubes (CNTs)-hybrids (Co3O4/MnO2-CNTs) have been successfully developed through a facile two-pot precipitation reaction and hydrothermal process, which exhibit the superior bi-functional catalytic activity for both ORR and OER. The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes, hollow Co3O4 and CNTs, which can produce a synergetic enhancement. When integrated into the practical primary and electrochemically rechargeable Zn-air batteries, such a hybrid catalyst can give a discharge peak power density as high as 450 mW cm(-2). At 1.0 V of cell voltage, a current density of 324 mA cm(-2) is achieved. This performance is superior to all reported non-precious metal catalysts in literature for zinc-air batteries and significantly outperforms the state-of-the-art platinum-based catalyst. Particularly, the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach, which exhibits an excellent peak power density of 62 mW cm(-2), and the charge and discharge potentials remain virtually unchanged during the overall cycles, which is comparable to the one with liquid electrolyte.

  4. Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery

    PubMed Central

    Xu, Nengneng; Liu, Yuyu; Zhang, Xia; Li, Xuemei; Li, Aijun; Qiao, Jinli; Zhang, Jiujun

    2016-01-01

    α-MnO2 nanotubes-supported Co3O4 (Co3O4/MnO2) and its carbon nanotubes (CNTs)-hybrids (Co3O4/MnO2-CNTs) have been successfully developed through a facile two-pot precipitation reaction and hydrothermal process, which exhibit the superior bi-functional catalytic activity for both ORR and OER. The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes, hollow Co3O4 and CNTs, which can produce a synergetic enhancement. When integrated into the practical primary and electrochemically rechargeable Zn-air batteries, such a hybrid catalyst can give a discharge peak power density as high as 450 mW cm−2. At 1.0 V of cell voltage, a current density of 324 mA cm−2 is achieved. This performance is superior to all reported non-precious metal catalysts in literature for zinc-air batteries and significantly outperforms the state-of-the-art platinum-based catalyst. Particularly, the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach, which exhibits an excellent peak power density of 62 mW cm−2, and the charge and discharge potentials remain virtually unchanged during the overall cycles, which is comparable to the one with liquid electrolyte. PMID:27646032

  5. Self-assembly formation of Bi-functional Co3O4/MnO2-CNTs hybrid catalysts for achieving both high energy/power density and cyclic ability of rechargeable zinc-air battery

    NASA Astrophysics Data System (ADS)

    Xu, Nengneng; Liu, Yuyu; Zhang, Xia; Li, Xuemei; Li, Aijun; Qiao, Jinli; Zhang, Jiujun

    2016-09-01

    α-MnO2 nanotubes-supported Co3O4 (Co3O4/MnO2) and its carbon nanotubes (CNTs)-hybrids (Co3O4/MnO2-CNTs) have been successfully developed through a facile two-pot precipitation reaction and hydrothermal process, which exhibit the superior bi-functional catalytic activity for both ORR and OER. The high performance is believed to be induced by the hybrid effect among MnO2 nanotubes, hollow Co3O4 and CNTs, which can produce a synergetic enhancement. When integrated into the practical primary and electrochemically rechargeable Zn-air batteries, such a hybrid catalyst can give a discharge peak power density as high as 450 mW cm‑2. At 1.0 V of cell voltage, a current density of 324 mA cm‑2 is achieved. This performance is superior to all reported non-precious metal catalysts in literature for zinc-air batteries and significantly outperforms the state-of-the-art platinum-based catalyst. Particularly, the rechargeable Zn-air battery can be fabricated into all-solid-state one through a simple solid-state approach, which exhibits an excellent peak power density of 62 mW cm‑2, and the charge and discharge potentials remain virtually unchanged during the overall cycles, which is comparable to the one with liquid electrolyte.

  6. Effects of elevated ozone concentration on CH4 and N2O emission from paddy soil under fully open-air field conditions.

    PubMed

    Tang, Haoye; Liu, Gang; Zhu, Jianguo; Kobayashi, Kazuhiko

    2015-04-01

    We investigated the effects of elevated ozone concentration (E-O3) on CH4 and N2O emission from paddies with two rice cultivars: an inbred Indica cultivar Yangdao 6 (YD6) and a hybrid one II-you 084 (IIY084), under fully open-air field conditions in China. A mean 26.7% enhancement of ozone concentration above the ambient level (A-O3) significantly reduced CH4 emission at tillering and flowering stages leading to a reduction of seasonal integral CH4 emission by 29.6% on average across the two cultivars. The reduced CH4 emission is associated with O3-induced reduction in the whole-plant biomass (-13.2%), root biomass (-34.7%), and maximum tiller number (-10.3%), all of which curbed the carbon supply for belowground CH4 production and its release from submerged soil to atmosphere. Although no significant difference was detected between the cultivars in the CH4 emission response to E-O3, a larger decrease in CH4 emission with IIY084 (-33.2%) than that with YD6 (-7.0%) was observed at tillering stage, which may be due to the larger reduction in tiller number in IIY084 by E-O3. Additionally, E-O3 reduced seasonal mean NOx flux by 5.7% and 11.8% with IIY084 and YD6, respectively, but the effects were not significant statistically. We found that the relative response of CH4 emission to E-O3 was not significantly different from those reported in open-top chamber experiments. This study has thus confirmed that increasing ozone concentration would mitigate the global warming potential of CH4 and suggested consideration of the feedback mechanism between ozone and its precursor emission into the projection of future ozone effects on terrestrial ecosystem.

  7. Free-air CO2 enrichment (FACE) reduces the inhibitory effect of soil nitrate on N2 fixation of Pisum sativum

    PubMed Central

    Butterly, Clayton R.; Armstrong, Roger; Chen, Deli; Tang, Caixian

    2016-01-01

    Background and Aims Additional carbohydrate supply resulting from enhanced photosynthesis under predicted future elevated CO2 is likely to increase symbiotic nitrogen (N) fixation in legumes. This study examined the interactive effects of atmospheric CO2 and nitrate (NO3–) concentration on the growth, nodulation and N fixation of field pea (Pisum sativum) in a semi-arid cropping system. Methods Field pea was grown for 15 weeks in a Vertosol containing 5, 25, 50 or 90 mg NO3–-N kg–1 under either ambient CO2 (aCO2; 390 ppm) or elevated CO2 (eCO2; 550 ppm) using free-air CO2 enrichment (SoilFACE). Key Results Under aCO2, field pea biomass was significantly lower at 5 mg NO3–-N kg–1 than at 90 mg NO3–-N kg–1 soil. However, increasing the soil N level significantly reduced nodulation of lateral roots but not the primary root, and nodules were significantly smaller, with 85 % less nodule mass in the 90 NO3–-N kg–1 than in the 5 mg NO3–-N kg–1 treatment, highlighting the inhibitory effects of NO3–. Field pea grown under eCO2 had greater biomass (approx. 30 %) than those grown under aCO2, and was not affected by N level. Overall, the inhibitory effects of NO3– on nodulation and nodule mass appeared to be reduced under eCO2 compared with aCO2, although the effects of CO2 on root growth were not significant. Conclusions Elevated CO2 alleviated the inhibitory effect of soil NO3– on nodulation and N2 fixation and is likely to lead to greater total N content of field pea growing under future elevated CO2 environments. PMID:26346721

  8. Fabrication of Bi2O3/TiO2 nanocomposites and their applications to the degradation of pollutants in air and water under visible-light.

    PubMed

    Chakraborty, Ashok Kumar; Hossain, Md Emran; Rhaman, Md Masudur; Sobahan, K M A

    2014-02-01

    A nanoheterojunction composite photocatalyst Bi2O3/TiO2 working under visible-light (lambda > or = 420 nm) was prepared by combining two semiconductors Bi2O3 and TiO2 varying the Bi2O3/TiO2 molar ratio. Maleic acid was employed as an organic binder to unite Bi2O3 and TiO2 nanoparticles. The SEM, TEM, XRD and diffuse reflectance spectra were utilized to characterize the prepared Bi2O3/TiO2 nanoheterojunction. The nanocomposite exhibited unusual high photocatalytic activity in decomposing 2-propanol in gas phase and phenol in aqueous phase and, evolution of CO2 under visible light irradiation while the end members exhibited low photocatalytic activity. The composite was optimized to 5 mol% Bi2O3/TiO2. The remarkable high photocatalytic efficiency originates from the unique relative energy band position of Bi2O3 and TiO2 as well as the absorption of visible light by Bi2O3.

  9. Perennial N2 supersaturation in an Antarctic lake. [biological processes in thin martian atmosphere

    NASA Technical Reports Server (NTRS)

    Wharton, Robert A., Jr.; Mckay, Christopher P.; Mancinelli, Rocco L.; Simmons, George M., Jr.

    1987-01-01

    The results of a study are reported which, for the first time, documents the supersaturation of N2 in a lake. Dissolved N2 levels of 145 percent and 163 percent were determined for Antarctica's Lake Hoare from samples taken just below the ice cover and at a depth of 12 m, respectively. The relative importance of biological and abiological sources is reflected in the ratio of N2 concentration to O2 concentration. In Lake Hoare this ratio was 1.20 at the ice/water interface and 1.05 at 12 m, considerably different from the ratio in equilibrium with air (about 1.8). Based on these results, it is determined that about half of the net O2 production in the lake is the result of biological processes. The significance of these results for the putative ice-covered paleolakes in the canyon regions of Mars is discussed.

  10. Impacts on Air Quality due to Photosensitized Production of Excited State O2 (1Δg) by PAHs and Oxy-PAHs in the Lower Atmosphere: An Experimental and Computational Modeling Approach

    NASA Astrophysics Data System (ADS)

    Montoya, G. A.; Carreras-Sospedra, M.; Montoya, J.; Dabdub, D.; Foster, K. L.

    2014-12-01

    Complex reactions between hydroxyl radicals (OH) and volatile organic compounds (VOCs) in the lower atmosphere have a high impact on the formation/fates of airborne toxic chemicals, polycyclic aromatic hydrocarbons (PAHs), and particulate matter.1 Recently, air quality models have been implemented to identify OH sources, but have underpredicted OH concentrations. Studies suggest that O2 (1Δg) is produced via an energy transfer (ET) mechanism initiated by the electronic excitation of PAH and oxygenated-PAH. Energy transfer involves the formation of triplet excited state PAH which is then quenched by the surrounding ground state O2 (3∑g) resulting in excited state O2 (1Δg) formation. Excited state O2 (1Δg) is known to readily react with mono-olefins to produce organic hydroperoxides.2,3 Furthermore, the organic hydroperoxide can photodegrade to yield OH. In this study, a Nd:YAG laser coupled to a time-resolved near infrared detector was used to obtain quantum yields of O2 (1Δg) production by irradiating PAHs and oxy-PAHs at both 355 nm and 532 nm in different solvents. Select PAHs, primarily emitted by combustion engines (e.g. pyrene and benzo[a]pyrene), and their oxygenated forms (oxy-PAHs) have been identified as highly efficient O2 (1Δg) photosensitizers. For example, the measured quantum yield for pyrene in toluene was 0.90 ± 0.02. The measured quantum yields were used to calculate the photochemical rate constants for O2 (1Δg) production via ET from electronically excited PAHs and oxy-PAHs. These results were incorporated into the University of California, Irvine-California Institute of Technology (UCI-CIT) model to assess the impact on OH concentrations and the overall air quality of the South Coast Air Basin of California. References 1 Finlayson-Pitts, B.J., and J. N. Pitts (1997), Science, 276(5315),1045-1052. 2 Foote, C. S. (1968), Accts. Chem. Res., 1, 104-110; Gollnick, K. (1968), Adv. Photochem., 6, 1-112; Kearns, D. R. (1971), Chem. Rev., 71, 395

  11. Computation provides chemical insight into the diverse hydride NMR chemical shifts of [Ru(NHC)4(L)H](0/+) species (NHC = N-heterocyclic carbene; L = vacant, H2, N2, CO, MeCN, O2, P4, SO2, H(-), F(-) and Cl(-)) and their [Ru(R2PCH2CH2PR2)2(L)H](+) congeners.

    PubMed

    Häller, L Jonas L; Mas-Marzá, Elena; Cybulski, Mateusz K; Sanguramath, Rajashekharayya A; Macgregor, Stuart A; Mahon, Mary F; Raynaud, Christophe; Russell, Christopher A; Whittlesey, Michael K

    2017-02-28

    Relativistic density functional theory calculations, both with and without the effects of spin-orbit coupling, have been employed to model hydride NMR chemical shifts for a series of [Ru(NHC)4(L)H](0/+) species (NHC = N-heterocyclic carbene; L = vacant, H2, N2, CO, MeCN, O2, P4, SO2, H(-), F(-) and Cl(-)), as well as selected phosphine analogues [Ru(R2PCH2CH2PR2)2(L)H](+) (R = (i)Pr, Cy; L = vacant, O2). Inclusion of spin-orbit coupling provides good agreement with the experimental data. For the NHC systems large variations in hydride chemical shift are shown to arise from the paramagnetic term, with high net shielding (L = vacant, Cl(-), F(-)) being reinforced by the contribution from spin-orbit coupling. Natural chemical shift analysis highlights the major orbital contributions to the paramagnetic term and rationalizes trends via changes in the energies of the occupied Ru dπ orbitals and the unoccupied σ*Ru-H orbital. In [Ru(NHC)4(η(2)-O2)H](+) a δ-interaction with the O2 ligand results in a low-lying LUMO of dπ character. As a result this orbital can no longer contribute to the paramagnetic shielding, but instead provides additional deshielding via overlap with the remaining (occupied) dπ orbital under the Lz angular momentum operator. These two effects account for the unusual hydride chemical shift of +4.8 ppm observed experimentally for this species. Calculations reproduce hydride chemical shift data observed for [Ru((i)Pr2PCH2CH2P(i)Pr2)2(η(2)-O2)H](+) (δ = -6.2 ppm) and [Ru(R2PCH2CH2PR2)2H](+) (ca. -32 ppm, R = (i)Pr, Cy). For the latter, the presence of a weak agostic interaction trans to the hydride ligand is significant, as in its absence (R = Me) calculations predict a chemical shift of -41 ppm, similar to the [Ru(NHC)4H](+) analogues. Depending on the strength of the agostic interaction a variation of up to 18 ppm in hydride chemical shift is possible and this factor (that is not necessarily readily detected experimentally) can aid in the

  12. Partial oxidation of methanol catalyzed with Au/TiO2, Au/ZrO2 and Au/ZrO2-TiO2 catalysts

    NASA Astrophysics Data System (ADS)

    Hernández-Ramírez, E.; Wang, J. A.; Chen, L. F.; Valenzuela, M. A.; Dalai, A. K.

    2017-03-01

    Mesoporous TiO2, ZrO2 and ZrO2-TiO2 mixed oxides were synthesized by the sol-gel method and the Au/TiO2, Au/ZrO2 and Au/ZrO2-TiO2 catalysts were prepared by deposition-precipitation method using urea solution as a precipitating agent. These materials were characterized by UV-vis spectroscopy, X-ray diffraction (XRD), N2 adsorption-desorption isotherms, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and in situ FTIR-pyridine (FTIR-Py) adsorption. XRD patterns of the samples confirmed the formation of ZrTiO4 phase in the ZrO2-TiO2 mixed oxides. TEM micrographs showed that nanosized gold particles on the catalyst had an average diameter smaller than 5 nm. Metallic gold (Au0) and oxidized Au species (Aunδ+) on the surface of the catalysts were evidenced by UV-vis and XPS characterization. In the partial oxidation of methanol (POM) reaction, among the six catalysts, the high metallic Au0/Au+ ratio and low surface acidity in the Au/ZrO2 catalysts are chiefly responsible for the highest hydrogen production rate in the whole temperature range between 210 and 300 °C. Methanol decomposition as secondary reaction was favored on TiO2-based catalysts at higher temperature, producing a large amount of CO. Formation of ZrO2-TiO2 solid solution resulted in generation of both Brønsted and Lewis acid sites; as a result, dehydrogenation and oxidative dehydrogenation of methanol was allowed over Au/ZrO2-TiO2 catalysts.

  13. Free-air CO2 enrichment (FACE) reduces the inhibitory effect of soil nitrate on N2 fixation of Pisum sativum.

    PubMed

    Butterly, Clayton R; Armstrong, Roger; Chen, Deli; Tang, Caixian

    2016-01-01

    Additional carbohydrate supply resulting from enhanced photosynthesis under predicted future elevated CO2 is likely to increase symbiotic nitrogen (N) fixation in legumes. This study examined the interactive effects of atmospheric CO2 and nitrate (NO3(-)) concentration on the growth, nodulation and N fixation of field pea (Pisum sativum) in a semi-arid cropping system. Field pea was grown for 15 weeks in a Vertosol containing 5, 25, 50 or 90 mg NO3(-)-N kg(-1) under either ambient CO2 (aCO2; 390 ppm) or elevated CO2 (eCO2; 550 ppm) using free-air CO2 enrichment (SoilFACE). Under aCO2, field pea biomass was significantly lower at 5 mg NO3(-)-N kg(-1) than at 90 mg NO3(-)-N kg(-1) soil. However, increasing the soil N level significantly reduced nodulation of lateral roots but not the primary root, and nodules were significantly smaller, with 85% less nodule mass in the 90 NO3(-)-N kg(-1) than in the 5 mg NO3(-)-N kg(-1) treatment, highlighting the inhibitory effects of NO3(-). Field pea grown under eCO2 had greater biomass (approx. 30%) than those grown under aCO2, and was not affected by N level. Overall, the inhibitory effects of NO3(-) on nodulation and nodule mass appeared to be reduced under eCO2 compared with aCO2, although the effects of CO2 on root growth were not significant. Elevated CO2 alleviated the inhibitory effect of soil NO3(-) on nodulation and N2 fixation and is likely to lead to greater total N content of field pea growing under future elevated CO2 environments. © The Author 2015. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  14. Markers of nucleic acids and proteins oxidation among office workers exposed to air pollutants including (nano)TiO2 particles.

    PubMed

    Pelclova, Daniela; Zdimal, Vladimir; Kacer, Petr; Vlckova, Stepanka; Fenclova, Zdenka; Navratil, Tomas; Komarc, Martin; Schwarz, Jaroslav; Zikova, Nadezda; Makes, Otakar; Zakharov, Sergey

    2016-12-18

    Experimental studies using nanoscale TiO2 have documented lung injury, inflammation, oxidative stress, and genotoxicity. Human health data are extremely scarce. In exhaled breath condensate (EBC) and urine of 22 office employees occupationally exposed to TiO2 during their visit in the production workshops for average 14±9 min/day a panel of biomarkers of nucleic acids and proteins oxidation was studied, specifically 8-hydroxy-2-deoxyguanosine (8-OHdG), 8-hydroxyguanosine (8-OHG), 5-hydroxymethyl uracil (5-OHMeU), o-tyrosine (o-Tyr), 3-chlorotyrosine (3-ClTyr), and 3-nitrotyrosine (3-NOTyr). Examination was performed also in 14 comparable controls. The median respirable TiO2 mass concentration in the workshops was 0.40 mg/m3, median number concentration was 2.32×104 particles/cm3 with 80% of the particles being <100 nm in diameter. All 6 markers of oxidation were elevated in EBC in factory office employees relative to controls (p<0.01). Significant association was found between their job in TiO2 production plant and 5 markers of oxidation (except 3-NOTyr) in the EBC in multivariate analysis. No elevation of markers was detected in the urine. This pilot study suggests that even short nanoTiO2 exposure may lead to pulmonary oxidative stress; however this effect may be short-term and reversible. The clinical significance of these findings is unclear and more studies are needed.

  15. Probing the Self-Assembly Mechanism of Lanthanide-Containing Sandwich-Type Silicotungstates [{Ln(H2O)n}2{Mn4(B-α-SiW9O34)2(H2O)2}](6-) Using Time-Resolved Mass Spectrometry and X-ray Crystallography.

    PubMed

    Fan, Lin-Yuan; Lin, Zheng-Guo; Cao, Jie; Hu, Chang-Wen

    2016-03-21

    The reaction of [γ-SiW10O36](8-) with Mn(2+) and Ln(3+) in an aqueous solution led to the isolation of a series of new lanthanide-containing sandwich-type polyoxometalates (POMs) [{Ln(H2O)n}2{Mn4(B-α-SiW9O34)2(H2O)2}](6-) (1-5a) (Ln = La (1), Nd (2), Gd (3), Dy (4), Er (5); n = 5, 6), which crystallize in the space groups C2/c with a = 33.0900(2)-32.9838(15) Å, b = 12.8044(10)-12.7526(6) Å, c = 22.8273(17)-22.6368(11) Å, V = 9669.2(12)-9519.7(8) Å(3), Z = 2 (1, 2); P1̅ with a = 11.9502(4)-11.8447(6) Å, b = 13.2203(4)-13.1164(5) Å, c = 15.8291(5)-15.8524(7) Å, V = 2221.25(13)-2189.95(18) Å(3), Z = 1 (3, 4, 5), respectively. X-ray diffraction analysis reveals that they consist of two-dimensional networks based on a sandwich-type polyanion [Mn4(B-α-SiW9O34)2(H2O)2](12-) (6a, {Mn4(SiW9)2}) and lanthanide cations (Ln(3+)), which are further connected into three-dimensional frameworks by potassium cations for 3, 4, and 5. The unprecedented combination of time-resolved electrospray ionization mass spectrometry (ESI-MS) studies and X-ray crystallography allows us not only to directly observe the in-solution rearrangement of divant anion [γ-SiW10O36](8-) into the sandwich-type POM 6a via an intermediate species [Mn3(B-β-SiW8O30(OH))(B-β-SiW9O33(OH))(H2O)](12-) (7a, {Mn3(SiW8)(SiW9)}) from ESI-MS results, but also to gain the solid-state structures of intermediate and final product isolated from reaction solutions from X-ray crystallography results, from which the self-assembly mechanism of the lanthanide-containing sandwich-type POMs 1-5a was proposed.

  16. Extension of pulmonary O2 tolerance in man at 2 ATA by intermittent O2 exposure

    NASA Technical Reports Server (NTRS)

    Hendricks, P. L.; Hall, D. A.; Hunter, W. L., Jr.; Haley, P. J.

    1977-01-01

    To study extension of O2 tolerance by interruption of hyperoxic exposure, five healthy volunteers were exposed to oxygen at 2 ATA on an intermittent schedule of 20 min breathing O2, alternating with 5 min on a normoxic N2-O2 mixture. The cycle was repeated until symptoms or signs of O2 toxicity caused cessation of the experiment. Tracheal irritation and burning on inspiration occurred after 6-9 'oxygen hours' of exposure and progressed to severe tracheobronchial burning sensation, chest pain, and dyspnea after 11-15 h of O2. With intermittent O2 administration, nearly a doubling of the average duration of actual oxygen breathing was required to induce marked vital capacity change (more than 10%) as compared to the previous studies of continuous O2 exposure.

  17. Extension of pulmonary O2 tolerance in man at 2 ATA by intermittent O2 exposure

    NASA Technical Reports Server (NTRS)

    Hendricks, P. L.; Hall, D. A.; Hunter, W. L., Jr.; Haley, P. J.

    1977-01-01

    To study extension of O2 tolerance by interruption of hyperoxic exposure, five healthy volunteers were exposed to oxygen at 2 ATA on an intermittent schedule of 20 min breathing O2, alternating with 5 min on a normoxic N2-O2 mixture. The cycle was repeated until symptoms or signs of O2 toxicity caused cessation of the experiment. Tracheal irritation and burning on inspiration occurred after 6-9 'oxygen hours' of exposure and progressed to severe tracheobronchial burning sensation, chest pain, and dyspnea after 11-15 h of O2. With intermittent O2 administration, nearly a doubling of the average duration of actual oxygen breathing was required to induce marked vital capacity change (more than 10%) as compared to the previous studies of continuous O2 exposure.

  18. Desflurane usage during anesthesia with and without N2O using FLOW-i Automatic Gas Control with three different wash-in speeds.

    PubMed

    De Medts, Robrecht; Carette, Rik; De Wolf, Andre M; Hendrickx, Jan F A

    2017-06-09

    AGC(®) (Automatic Gas Control) is the FLOW-i's automated low flow tool (Maquet, Solna, Sweden) that target controls the inspired O2 (FIO2) and end-expired desflurane concentration (FAdes) while (by design) exponentially decreasing fresh gas flow (FGF) during wash-in to a maintenance default FGF of 300 mL min(-1). It also offers a choice of wash-in speeds for the inhaled agents. We examined AGC performance and hypothesized that the use of lower wash-in speeds and N2O both reduce desflurane usage (Vdes). After obtaining IRB approval and patient consent, 78 ASA I-II patients undergoing abdominal surgery were randomly assigned to 1 of 6 groups (n = 13 each), depending on