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Sample records for atmospheric reaction products

  1. Carbonyl atmospheric reaction products of aromatic hydrocarbons in ambient air

    NASA Astrophysics Data System (ADS)

    Obermeyer, Genevieve; Aschmann, Sara M.; Atkinson, Roger; Arey, Janet

    To convert gaseous carbonyls to oximes during sampling, an XAD-4 resin denuder system pre-coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine and followed by analysis with methane positive chemical ionization gas chromatography/mass spectrometry was used to measure carbonyls in ambient air samples in Riverside, CA. In conjunction with similar analyses of environmental chamber OH radical-initiated reactions of o- and p-xylene, 1,2,4-trimethylbenzene, ethylbenzene, 4-hydroxy-2-butanone and 1,4-butanediol, we identified benzaldehyde, o-, m- and p-tolualdehyde and acetophenone and the dicarbonyls glyoxal, methylglyoxal, biacetyl, ethylglyoxal, 1,4-butenedial, 3-hexene-2,5-dione, 3-oxo-butanal, 1,4-butanedial and malonaldehyde in the ambient air samples. As discussed, these carbonyls and dicarbonyls can be formed from the OH radical-initiated reactions of aromatic hydrocarbons and other volatile organic compounds emitted into the atmosphere, and we conclude that in situ atmospheric formation is a major source of these carbonyls in our Riverside, CA, ambient air samples.

  2. Studies of the Atmospheric Chemsitry of Energy-Related Volatile Organic Compounds and of their Atmospheric Reaction Products

    SciTech Connect

    Roger Atkinson; Janet Arey

    2007-04-14

    The focus of this contract was to investigate selected aspects of the atmospheric chemistry of volatile organic compounds (VOCs) emitted into the atmosphere from energy-related sources as well as from biogenic sources. The classes of VOCs studied were polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs, the biogenic VOCs isoprene, 2-methyl-3-buten-2-ol and cis-3-hexen-1-ol, alkenes (including alkenes emitted from vegetation) and their oxygenated atmospheric reaction products, and a series of oxygenated carbonyl and hydroxycarbonyl compounds formed as atmospheric reaction products of aromatic hydrocarbons and other VOCs. Large volume reaction chambers were used to investigate the kinetics and/or products of photolysis and of the gas-phase reactions of these organic compounds with hydroxyl (OH) radicals, nitrate (NO3) radicals, and ozone (O3), using an array of analytical instrumentation to analyze the reactants and products (including gas chromatography, in situ Fourier transform infrared spectroscopy, and direct air sampling atmospheric pressure ionization tandem mass spectrometry). The following studies were carried out. The photolysis rates of 1- and 2-nitronaphthalene and of eleven isomeric methylnitronaphthalenes were measured indoors using blacklamp irradiation and outdoors using natural sunlight. Rate constants were measured for the gas-phase reactions of OH radicals, Cl atoms and NO3 radicals with naphthalene, 1- and 2-methylnaphthalene, 1- and 2-ethylnaphthalene and the ten dimethylnaphthalene isomers. Rate constants were measured for the gas-phase reactions of OH radicals with four unsaturated carbonyls and with a series of hydroxyaldehydes formed as atmospheric reaction products of other VOCs, and for the gas-phase reactions of O3 with a series of cycloalkenes. Products of the gas-phase reactions of OH radicals and O3 with a series of biogenically emitted VOCs were identified and quantified. Ambient atmospheric measurements of the concentrations of a

  3. The Reaction of Criegee Intermediate CH2OO with Water Dimer: Primary Products and Atmospheric Impact

    DOE PAGES

    Sheps, Leonid; Rotavera, Brandon; Eskola, Arkke J.; ...

    2017-08-04

    The rapid reaction of the smallest Criegee intermediate, CH2OO, with water dimers is the dominant removal mechanism for CH2OO in the Earth's atmosphere, but its products are not well understood. This reaction was recently suggested as a significant source of the most abundant tropospheric organic acid, formic acid (HCOOH), which is consistently underpredicted by atmospheric models. Furthermore, using time-resolved measurements of reaction kinetics by UV absorption and product analysis by photoionization mass spectrometry, we show that the primary products of this reaction are formaldehyde and hydroxymethyl hydroperoxide (HMHP), with direct HCOOH yields of less than 10%. Incorporating our results intomore » a global chemistry-transport model further reduces HCOOH levels by 10–90%, relative to previous modeling assumptions, which indicates that the reaction CH2OO + water dimer by itself cannot resolve the discrepancy between the measured and predicted HCOOH levels.« less

  4. Kinetic and Product Yields of the Gas-Phase Reactions of Isoprene Hydroperoxides with Atmospheric Oxidants

    NASA Astrophysics Data System (ADS)

    Kumar, V.; Lozano, E. I.; Maitra, S.; Manning, D. M.; Cervantes, R.; Hasson, A. S.

    2015-12-01

    Isoprene is a volatile organic compound (VOC) that is emitted into the atmosphere by plants and trees. It has the largest emission rate of any non-methane VOC and is very reactive, and therefore has a major impact on the chemical composition of the atmosphere. Isoprene Hydroperoxides (IHP) are formed in the atmosphere from the chemical degradation of isoprene. These compounds can then potentially react in the atmosphere with atmospheric oxidants (ozone, OH, NO3) to produce secondary products. This chemistry is potentially important as it may contribute to particle growth and to mediation of ozone concentrations. In this work, the kinetics and mechanisms of the reactions of two IHPs with ozone were investigated. IHPs were synthesized and purified, and were characterized by NMR and HPLC. The gas phase chemistry of these compounds was then studied in chamber experiments using PTRMS as the primary analytical tool. The rate coefficients for reaction with ozone were measured at room temperature and 1 atmosphere using the relative rate technique, and yields of major gas phase reaction products were measured. Implications of these results will be discussed.

  5. Atmospheric reactions of gaseous mercury with ozone and hydroxyl radical: Kinetics and product studies

    NASA Astrophysics Data System (ADS)

    Biswajit, P.; Parisa, A. A.

    2003-05-01

    The dominant form of mercury in the atmosphere is Hg^0. The oxidation processes are of great importance since oxidized mercury undergoes deposition and can become subject to bioaccumulation. Experimental data on the gaseous reactions of elemental mercury are very limited with compare to the reactions of Hg^0 in solutions. We herein carried out kinetic and product studies on the reactions of gaseous Hg^0 with O3 and hydroxyl radical (HO) under near atmospheric pressure (750 ± 1 Torr) and room temperature (298 ± 1 K) in air and N2. O3 was produced in a silent discharge generator (OL 100/SB). Hydroxyl radicals were produced from the photolysis of isopropyl nitrite in the presence of NO. Kinetics of the reactions with O3/HO was studied using absolute and relative techniques by gas chromatography with mass spectroscopic detection (GCMS). The gas phase reaction between elemental Hg^0 with O3 has been studied in different surface-to-volume (s/v) ratios, and evidence for heterogeneous reactions was observed. Existence of mercuric oxide, Hg^0 by the reaction of atomic Hg^0 with O3 has been determined in the gas phase from the suspended aerosols using high temperature mass spectrometry.

  6. Productions of Volatile Organic Compounds (VOCs) in Surface Waters from Reactions with Atmospheric Ozone

    NASA Astrophysics Data System (ADS)

    Hopkins, Frances; Bell, Thomas; Yang, Mingxi

    2017-04-01

    Ozone (O3) is a key atmospheric oxidant, greenhouse gas and air pollutant. In marine environments, some atmospheric ozone is lost by reactions with aqueous compounds (e.g. dissolved organic material, DOM, dimethyl sulfide, DMS, and iodide) near the sea surface. These reactions also lead to formations of volatile organic compounds (VOCs). Removal of O3 by the ocean remains a large uncertainty in global and regional chemical transport models, hampering coastal air quality forecasts. To better understand the role of the ocean in controlling O3 concentrations in the coastal marine atmosphere, we designed and implemented a series of laboratory experiments whereby ambient surface seawater was bubbled with O3-enriched, VOC-free air in a custom-made glass bubble equilibration system. Gas phase concentrations of a range of VOCs were monitored continuously over the mass range m/z 33 - 137 at the outflow of the bubble equilibrator by a proton transfer reaction - mass spectrometer (PTR-MS). Gas phase O3 was also measured at the input and output of the equilibrator to monitor the uptake due to reactions with dissolved compounds in seawater. We observed consistent productions of a variety of VOCs upon reaction with O3, notably isoprene, aldehydes, and ketones. Aqueous DMS is rapidly removed from the reactions with O3. To test the importance of dissolved organic matter precursors, we added increasing (milliliter) volumes of Emiliania huxleyi culture to the equilibrator filled with aged seawater, and observed significant linear increases in gas phase concentrations of a number of VOCs. Reactions between DOM and O3 at the sea-air interface represent a potentially significant source of VOCs in marine air and a sink of atmospheric O3.

  7. The reaction between CH3O2 and OH radicals: Product yields and atmospheric implications

    DOE PAGES

    Assaf, Emmanuel; Sheps, Leonid; Whalley, Lisa; ...

    2017-01-25

    The reaction between CH3O2 and OH radicals has been shown to be fast and to play an appreciable role for the removal of CH3O2 radials in remote environments such as the marine boundary layer. Two different experimental techniques have been used here to determine the products of this reaction. The HO2 yield has been obtained from simultaneous time-resolved measurements of the absolute concentration of CH3O2, OH, and HO2 radicals by cw-CRDS. The possible formation of a Criegee intermediate has been measured by broadband cavity enhanced UV absorption. A yield of ΦHO2 = (0.8 ± 0.2) and an upper limit formore » ΦCriegee = 0.05 has been determined for this reaction, suggesting a minor yield of methanol or stabilized trioxide as a product. The impact of this reaction on the composition of the remote marine boundary layer has been determined by implementing these findings into a box model utilizing the Master Chemical Mechanism v3.2, and constraining the model for conditions found at the Cape Verde Atmospheric Observatory in the remote tropical Atlantic Ocean. Inclusion of the CH3O2+OH reaction into the model results in up to 30% decrease in the CH3O2 radical concentration while the HO2 concentration increased by up to 20%. Finally, production and destruction of O3 are also influenced by these changes, and the model indicates that taking into account the reaction between CH3O2 and OH leads to a 6% decrease of O3.« less

  8. The Reaction between CH3O2 and OH Radicals: Product Yields and Atmospheric Implications.

    PubMed

    Assaf, Emmanuel; Sheps, Leonid; Whalley, Lisa; Heard, Dwayne; Tomas, Alexandre; Schoemaecker, Coralie; Fittschen, Christa

    2017-02-21

    The reaction between CH3O2 and OH radicals has been shown to be fast and to play an appreciable role for the removal of CH3O2 radials in remote environments such as the marine boundary layer. Two different experimental techniques have been used here to determine the products of this reaction. The HO2 yield has been obtained from simultaneous time-resolved measurements of the absolute concentration of CH3O2, OH, and HO2 radicals by cw-CRDS. The possible formation of a Criegee intermediate has been measured by broadband cavity enhanced UV absorption. A yield of ϕHO2 = (0.8 ± 0.2) and an upper limit for ϕCriegee = 0.05 has been determined for this reaction, suggesting a minor yield of methanol or stabilized trioxide as a product. The impact of this reaction on the composition of the remote marine boundary layer has been determined by implementing these findings into a box model utilizing the Master Chemical Mechanism v3.2, and constraining the model for conditions found at the Cape Verde Atmospheric Observatory in the remote tropical Atlantic Ocean. Inclusion of the CH3O2+OH reaction into the model results in up to 30% decrease in the CH3O2 radical concentration while the HO2 concentration increased by up to 20%. Production and destruction of O3 are also influenced by these changes, and the model indicates that taking into account the reaction between CH3O2 and OH leads to a 6% decrease of O3.

  9. Pressure Effects on Product Channels of Hydrocarbon Radical-Radical Reactions; Implications for Modelling of Planetary Atmospheres

    NASA Astrophysics Data System (ADS)

    Fahr, A.; Halpern, J.; N'doumi, M.

    2011-10-01

    Previously we had studied the kinetics and product channels of small unsaturated hydrocarbon radical (C2 and C3s) reactions relevant to planetary atmospheric modelling. Reactions of C2 radicals (such as vinyl, H2CCH and ethynyl C2H) and C3 radicals (such as propargyl, HCCCH2 and allyl, H2CCCH3) can affect the abundances of a large number of stable observable C3, C4, C5, C6 and larger molecules, including linear, aromatic and even poly aromatic molecules. We have experimentally determined pressuredependent product yields for self- and cross-radical reactions performed at 298 K and at selected pressures between ~4 Torr (0.5 kPa) and 760 Torr (101 kPa). Final products were determined by gas chromatograph with mass spectrometry/flame ionization detection (GC/MS/FID). In some cases complementary computational studies extended the pressure and temperature range of the observations and provided valuable information on complex reaction mechanisms. These studies provide a systematic framework so that important energetic and structural parameters for radical-radical reactions can be assessed. Here we report a compilation of our earlier results relevant to planetary atmospheres in addition to recent ones for allyl radical (H2CCCH3) reactions.

  10. Structural and mechanical characterization of detonation coatings formed by reaction products of titanium with components of the spraying atmosphere

    NASA Astrophysics Data System (ADS)

    Ulianitsky, Vladimir Yu.; Dudina, Dina V.; Panin, Sergey V.; Vlasov, Ilya V.; Batraev, Igor S.; Bokhonov, Boris B.

    2016-11-01

    Structural characterization of detonation deposits formed by reaction products of titanium with the components of the spraying atmosphere showed that ceramic-based coatings of unique microstructures—consisting of alternating layers of different compositions—can be formed. For the first time, mechanical characteristics of the coatings formed by reaction-accompanied detonation spraying of titanium were evaluated. It was found that high-yield transformation of titanium into oxides and nitrides during spraying can result in the formation of coatings with high fracture resistance and interface fracture toughness. The hardness of the coatings measured along the cross-section of the specimens was higher than that on the surface of the coatings, which indicated mechanical anisotropy of the deposited material. In terms of mechanical properties, coatings formed by the reaction products appear to be more attractive than those specially treated to preserve metallic titanium.

  11. Atmospheric reactions of methylcyclohexanes with Cl atoms and OH radicals: determination of rate coefficients and degradation products.

    PubMed

    Ballesteros, Bernabé; Ceacero-Vega, Antonio A; Jiménez, Elena; Albaladejo, José

    2015-04-01

    As the result of biogenic and anthropogenic activities, large quantities of chemical compounds are emitted into the troposphere. Alkanes, in general, and cycloalkanes are an important chemical class of hydrocarbons found in diesel, jet and gasoline, vehicle exhaust emissions, and ambient air in urban areas. In general, the primary atmospheric fate of organic compounds in the gas phase is the reaction with hydroxyl radicals (OH). The oxidation by Cl atoms has gained importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments, and in the Arctic troposphere. The aim of this paper is to study of the atmospheric reactivity of methylcylohexanes with Cl atoms and OH radicals under atmospheric conditions (in air at room temperature and pressure). Relative kinetic techniques have been used to determine the rate coefficients for the reaction of Cl atoms and OH radicals with methylcyclohexane, cis-1,4-dimethylcyclohexane, trans-1,4-dimethylcyclohexane, and 1,3,5-trimethylcyclohexane at 298 ± 2 K and 720 ± 5 Torr of air by Fourier transform infrared) spectroscopy and gas chromatography-mass spectrometry (GC-MS) in two atmospheric simulation chambers. The products formed in the reaction under atmospheric conditions were investigated using a 200-L Teflon bag and employing the technique of solid-phase microextraction coupled to a GC-MS. The rate coefficients obtained for the reaction of Cl atoms with the studied compounds are the following ones (in units of 10(-10) cm(3) molecule(-1) s(-1)): (3.11 ± 0.16), (2.89 ± 0.16), (2.89 ± 0.26), and (2.61 ± 0.42), respectively. For the reactions with OH radicals the determined rate coefficients are (in units of 10(-11) cm(3) molecule(-1) s(-1)): (1.18 ± 0.12), (1.49 ± 0.16), (1.41 ± 0.15), and (1.77 ± 0.23), respectively. The reported error is twice the standard deviation. A detailed

  12. Secondary organic aerosol production from aqueous reactions of atmospheric phenols with an organic triplet excited state.

    PubMed

    Smith, Jeremy D; Sio, Vicky; Yu, Lu; Zhang, Qi; Anastasio, Cort

    2014-01-21

    Condensed-phase chemistry plays a significant role in the formation and evolution of atmospheric organic aerosols. Past studies of the aqueous photoformation of secondary organic aerosol (SOA) have largely focused on hydroxyl radical oxidation, but here we show that triplet excited states of organic compounds ((3)C*) can also be important aqueous oxidants. We studied the aqueous photoreactions of three phenols (phenol, guaiacol, and syringol) with the aromatic carbonyl 3,4-dimethoxybenzaldehyde (DMB); all of these species are emitted by biomass burning. Under simulated sunlight, DMB forms a triplet excited state that rapidly oxidizes phenols to form low-volatility SOA. Rate constants for these reactions are fast and increase with decreasing pH and increasing methoxy substitution of the phenols. Mass yields of aqueous SOA are near 100% for all three phenols. For typical ambient conditions in areas with biomass combustion, the aqueous oxidation of phenols by (3)C* is faster than by hydroxyl radical, although rates depend strongly on pH, oxidant concentrations, and the identity of the phenol. Our results suggest that (3)C* can be the dominant aqueous oxidant of phenols in areas impacted by biomass combustion and that this is a significant pathway for forming SOA.

  13. The acid-catalyzed hydrolysis of an α-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact

    NASA Astrophysics Data System (ADS)

    Rindelaub, Joel D.; Borca, Carlos H.; Hostetler, Matthew A.; Slade, Jonathan H.; Lipton, Mark A.; Slipchenko, Lyudmila V.; Shepson, Paul B.

    2016-12-01

    The production of atmospheric organic nitrates (RONO2) has a large impact on air quality and climate due to their contribution to secondary organic aerosol and influence on tropospheric ozone concentrations. Since organic nitrates control the fate of gas phase NOx (NO + NO2), a byproduct of anthropogenic combustion processes, their atmospheric production and reactivity is of great interest. While the atmospheric reactivity of many relevant organic nitrates is still uncertain, one significant reactive pathway, condensed phase hydrolysis, has recently been identified as a potential sink for organic nitrate species. The partitioning of gas phase organic nitrates to aerosol particles and subsequent hydrolysis likely removes the oxidized nitrogen from further atmospheric processing, due to large organic nitrate uptake to aerosols and proposed hydrolysis lifetimes, which may impact long-range transport of NOx, a tropospheric ozone precursor. Despite the atmospheric importance, the hydrolysis rates and reaction mechanisms for atmospherically derived organic nitrates are almost completely unknown, including those derived from α-pinene, a biogenic volatile organic compound (BVOC) that is one of the most significant precursors to biogenic secondary organic aerosol (BSOA). To better understand the chemistry that governs the fate of particle phase organic nitrates, the hydrolysis mechanism and rate constants were elucidated for several organic nitrates, including an α-pinene-derived organic nitrate (APN). A positive trend in hydrolysis rate constants was observed with increasing solution acidity for all organic nitrates studied, with the tertiary APN lifetime ranging from 8.3 min at acidic pH (0.25) to 8.8 h at neutral pH (6.9). Since ambient fine aerosol pH values are observed to be acidic, the reported lifetimes, which are much shorter than that of atmospheric fine aerosol, provide important insight into the fate of particle phase organic nitrates. Along with rate constant

  14. Reaction products and mechanisms for the reaction of n-butyl vinyl ether with the oxidants OH and Cl: Atmospheric implications

    NASA Astrophysics Data System (ADS)

    Colmenar, Inmaculada; Martín, Pilar; Cabañas, Beatriz; Salgado, Sagrario; Tapia, Araceli; Martínez, Ernesto

    2015-12-01

    A reaction product study for the degradation of butyl vinyl ether (CH3(CH2)3OCHdbnd CH2) by reaction with chlorine atoms (Cl) and hydroxyl radicals (OH) has been carried out using Fourier Transform Infrared absorption spectroscopy (FTIR) and/or Gas Chromatography-Mass Spectrometry with a Time of Flight analyzer (GC-TOFMS). The rate coefficient for the reaction of butyl vinyl ether (BVE) with chlorine atoms has also been evaluated for the first time at room temperature (298 ± 2) K and atmospheric pressure (708 ± 8) Torr. The rate coefficient obtained was (9.9 ± 1.5) × 10-10 cm3 molecule-1 s-1 and this indicates the high reactivity of butyl vinyl ether with Cl atoms. However, this value may be affected by the dark reaction of BVE with Cl2. The results of a qualitative study of the Cl reaction show that the main oxidation products are butyl formate (CH3(CH2)3OC(O)H), butyl chloroacetate (CH3(CH2)3OC(O)CH2Cl and formyl chloride (HCOCl). Individual yields in the ranges ∼16-40% and 30-70% in the absence and presence of NOx, respectively, have been estimated for these products. In the OH reaction, butyl formate and formic acid were identified as the main products, with yields of around 50 and 20%, respectively. Based on the results of this work and a literature survey, the addition of OH radicals and Cl atoms at the terminal C atom of the double bond in CH3(CH2)3OCHdbnd CH2 has been proposed as the first step in the reaction mechanism for both of the studied oxidants. The tropospheric lifetime of butyl vinyl ether is very short and, as a consequence, it will be rapidly degraded and will only be involved in tropospheric chemistry at a local level. The degradation products of these reactions should be considered when evaluating the atmospheric impact.

  15. The molecular dynamics of atmospheric reaction

    NASA Technical Reports Server (NTRS)

    Polanyi, J. C.

    1971-01-01

    Detailed information about the chemistry of the upper atmosphere took the form of quantitative data concerning the rate of reaction into specified states of product vibration, rotation and translation for exothermic reaction, as well as concerning the rate of reaction from specified states of reagent vibration, rotation and translation for endothermic reaction. The techniques used were variants on the infrared chemiluminescence method. Emphasis was placed on reactions that formed, and that removed, vibrationally-excited hydroxyl radicals. Fundamental studies were also performed on exothermic reactions involving hydrogen halides.

  16. Quantifying VOC-Reaction Tracers, Ozone Production, and Continuing Aerosol Production Rates in Urban and Far-Downwind Atmospheres

    NASA Technical Reports Server (NTRS)

    Chatfield, Robert; Ren, X.; Brune, W.; Fried, A.; Schwab, J.

    2008-01-01

    reaction products) and aerosol production, looking for VOC's that might be most implicated. All three variables j(sub rads), [HCHO], and [NO] are relatively easily measured in widespread air pollution monitoring networks, and all are deducible form space-borne observations, though estimation of [NO] from [NO2] (the species observable from space) may require care. We report also on airborne and surface observations of HCHO, suggesting that concentrated (urban) and more diffuse (forest) sources may be distinguishable from space. The use of the 3.58 micron microwindow for HCHO remote sensing should allow much sharper resolution of HCHO than the UV. UV sensing requires large and expensive instruments, but even these seem justified since formaldehyde is so informative.

  17. Quantifying VOC-Reaction Tracers, Ozone Production, and Continuing Aerosol Production Rates in Urban and Far-Downwind Atmospheres

    NASA Technical Reports Server (NTRS)

    Chatfield, Robert; Ren, X.; Brune, W.; Fried, A.; Schwab, J.

    2008-01-01

    reaction products) and aerosol production, looking for VOC's that might be most implicated. All three variables j(sub rads), [HCHO], and [NO] are relatively easily measured in widespread air pollution monitoring networks, and all are deducible form space-borne observations, though estimation of [NO] from [NO2] (the species observable from space) may require care. We report also on airborne and surface observations of HCHO, suggesting that concentrated (urban) and more diffuse (forest) sources may be distinguishable from space. The use of the 3.58 micron microwindow for HCHO remote sensing should allow much sharper resolution of HCHO than the UV. UV sensing requires large and expensive instruments, but even these seem justified since formaldehyde is so informative.

  18. Fading of alizarin and related artists's pigments by atmospheric ozone: reaction products and mechanisms

    SciTech Connect

    Grosjean, D.; Whitmore, P.M.; De Moor, C.P.; Cass, G.R.; Druzik, J.R.

    1987-07-01

    The colorants alizarin and Alizarin Crimson (a calcium-aluminum lake pigment) and their simple structural homologue anthraquinone were deposited on silica gel, cellulose, and Teflon substrates and exposed in the dark to ozone in purified air (approx.0.4 ppm O/sub 3/ for 95 days and approx.10 ppm O/sub 3/ for 18-80 h). Exposed and control samples were analyzed by mass spectrometry. Alizarin Crimson reacted with ozone on all substrates, yielding phthalic acid (major), benzoic acid (minor), and other minor and unidentified products. Anthraquinone did not react with ozone irrespective of conditions. Alizarin did not react on Teflon or cellulose but reacted on silica gel to yield phthalic acid (major) and other products. A chemical mechanism responsible for the fading of these alizarin-related colorants by ozone is suggested that is consistent with the products distribution, the observed reactivity sequence, and the observed substrate-specific effects. The possible application of this work to predicting the ozone fastness of other alizarin-related pigments is discussed briefly. 33 references, 5 figures.

  19. Atmospheric reactions of 9,10-anthraquinone.

    PubMed

    Miet, Killian; Albinet, Alexandre; Budzinski, Hélène; Villenave, Eric

    2014-07-01

    The probably carcinogenic compound 9,10-anthraquinone is mainly existing in the atmosphere in the particulate phase and is often detected and measured among other oxygenated PAHs in atmospheric samples. Its fate, once released or formed in the atmosphere, still remains unknown. In this work, heterogeneous chemical oxidation processes of 9,10-anthraquinone were investigated with ozone (O3), nitrogen dioxide (NO2) and hydroxyl radical (OH). The study of 9,10-anthraquinone adsorbed on silica particles showed no reactivity with O3 and NO2. On the other hand, the reaction with OH radicals was observed and led to the formation of 1-hydroxy-9,10-anthraquinone, another oxidation product recognized as possibly carcinogenic to humans. This study showed that reactions with ozone and nitrogen dioxide are unlikely to contribute to atmospheric degradation of 9,10-anthraquinone, whereas reactions with OH radicals could be involved in 9,10-anthraquinone degradation processes, even if such reaction is probably very slow under ambient conditions.

  20. Atmospheric Chemistry Data Products

    NASA Technical Reports Server (NTRS)

    2003-01-01

    This presentation poster covers data products from the Distributed Active Archive Center (DAAC) of the Goddard Earth Sciences (GES) Data and Information Services Center (DISC). Total Ozone Mapping Spectrometer products (TOMS) introduced in the presentation include TOMS Version 8 as well as Aura, which provides 25 years of TOMS and Upper Atmosphere Research Satellite (UARS) data. The presentation lists a number of atmospheric chemistry and dynamics data sets at DAAC.

  1. Atmospheric Chemistry of 1-Methoxy 2-Propyl Acetate: UV Absorption Cross Sections, Rate Coefficients, and Products of Its Reactions with OH Radicals and Cl Atoms.

    PubMed

    Zogka, Antonia G; Mellouki, Abdelwahid; Romanias, Manolis N; Bedjanian, Yuri; Idir, Mahmoud; Grosselin, Benoit; Daële, Véronique

    2016-11-17

    The rate coefficients for the reactions of OH and Cl with 1-methoxy 2-propyl acetate (MPA) in the gas phase were measured using absolute and relative methods. The kinetic study on the OH reaction was conducted in the temperature (263-373) K and pressure (1-760) Torr ranges using the pulsed laser photolysis-laser-induced fluorescence technique, a low pressure fast flow tube reactor-quadrupole mass spectrometer, and an atmospheric simulation chamber/GC-FID. The derived Arrhenius expression is kMPA+OH(T) = (2.01 ± 0.02) × 10(-12) exp[(588 ± 123/T)] cm(3) molecule(-1) s(-1). The absolute and relative rate coefficients for the reaction of Cl with MPA were measured at room temperature in the flow reactor and the atmospheric simulation chamber, which led to k(Cl+MPA) = (1.98 ± 0.31) × 10(-10) cm(3) molecule(-1) s(-1). GC-FID, GC-MS, and FT-IR techniques were used to investigate the reaction mechanism in the presence of NO. The products formed from the reaction of MPA with OH and their yields were methyl formate (80 ± 7.3%), acetic acid (50 ± 4.8%), and acetic anhydride (22 ± 2.4%), while for Cl reaction, the obtained yields were 60 ± 5.4, 41 ± 3.8, and 11 ± 1.2%, respectively, for the same products. The UV absorption cross section spectrum of MPA was determined in the wavelength range 210-370 nm. The study has shown no photolysis of MPA under atmospheric conditions. The obtained results are used to derive the atmospheric implication.

  2. The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system a review

    NASA Astrophysics Data System (ADS)

    Zahardis, J.; Petrucci, G. A.

    2006-11-01

    The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the primary products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. Anomalies in the relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide polymers. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei. The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, a series of atmospheric implications of oxidative processing of particulate containing fatty acids is presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semisolids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation. Other effects, including the potential role of aldehydic

  3. The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system - a review

    NASA Astrophysics Data System (ADS)

    Zahardis, J.; Petrucci, G. A.

    2007-02-01

    The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquid-phase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN). The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed

  4. Reactions of OH with. alpha. -pinene and. beta. -pinene in air: Estimate of global CO production from the atmosphere oxidation of terpenes

    SciTech Connect

    Hatakeyama, Shiro; Izumi, Katsuyuki; Fukuyama, Tsutomu; Akimoto, Hajime; Washida, Nobuaki )

    1991-01-20

    Reactions of OH with {alpha}-pinene and {beta}-pinene were studied for the purpose of obtaining the basic data to estimate the emission rate of CO from the photooxidation of terpenes in the atmosphere. In the presence of NO the main product was pinonaldehyde and 6,6-dimethylbicyclo(3.1.1)heptan-2-one from {alpha}- and {beta}-pinene, respectively, and the yield was 56{plus minus}4 and 79{plus minus}8%, respectively. In the absence of NO the yield was remarkably lower, and the yield of organic aerosols was enhanced. For {alpha}-pinene 56 {plus minus} 3% was obtained as a yield of aerosols on the carbon number basis. Gross annual emission of CO from the reactions of OH with terpenes was estimated to be 22 Tg C/yr (50 Tg CO/yr) by regarding {alpha}-pinene as the representative of terpenes, on the basis of the annual emission rate of terpenes, estimated lifetime of pinenes in the atmosphere, the apparent rate constant for the intermediate to form CO, and the estimated yield of CO from the secondary oxidation of pinonaldehyde. The ultimate yield of CO from the tropospheric oxidation of terpenes (including both ozone and OH reactions) was estimated to be 20% on the carbon number basis, and the total annual emission of CO was evaluated to be 96 Tg C/yr (222 Tg CO/yr).

  5. Atmospheric chemistry of t-CF3CH=CHCl: products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals.

    PubMed

    Andersen, M P Sulbaek; Nielsen, O J; Hurley, M D; Wallington, T J

    2012-02-07

    FTIR-smog chamber techniques were used to study the products and mechanisms of the Cl atom and OH radical initiated oxidation of trans-3,3,3-trifluoro-1-chloro-propene, t-CF(3)CH=CHCl, in 700 Torr of air or N(2)/O(2) diluent at 296 ± 2 K. The reactions of Cl atoms and OH radicals with t-CF(3)CH=CHCl occur via addition to the >C=C< double bond; chlorine atoms add 15 ± 5% at the terminal carbon and 85 ± 5% at the central carbon, OH radicals add approximately 40% at the terminal carbon and 60% at the central carbon. The major products in the Cl atom initiated oxidation of t-CF(3)CH=CHCl were CF(3)CHClCHO and CF(3)C(O)CHCl(2), minor products were CF(3)CHO, HCOCl and CF(3)COCl. The yields of CF(3)C(O)CHCl(2), CF(3)CHClCOCl and CF(3)COCl increased at the expense of CF(3)CHO, HCOCl and CF(3)CHClCHO as the O(2) partial pressure was increased over the range 10-700 Torr. Chemical activation plays a significant role in the fate of CF(3)CH(O)CHCl(2) and CF(3)CClHCHClO radicals. In addition to reaction with O(2) to yield CF(3)COCl and HO(2) the major competing fate of CF(3)CHClO is Cl elimination to give CF(3)CHO (not C-C bond scission as previously thought). As part of this study k(Cl + CF(3)C(O)CHCl(2)) = (2.3 ± 0.3) × 10(-14) and k(Cl + CF(3)CHClCHO) = (7.5 ± 2.0) × 10(-12) cm(3) molecule(-1) s(-1) were determined using relative rate techniques. Reaction with OH radicals is the major atmospheric sink for t-CF(3)CH=CHCl. Chlorine atom elimination giving the enol CF(3)CH=CHOH appears to be the sole atmospheric fate of the CF(3)CHCHClOH radicals. The yield of CF(3)COOH in the atmospheric oxidation of t-CF(3)CH=CHCl will be negligible (<2%). The results are discussed with respect to the atmospheric chemistry and environmental impact of t-CF(3)CH=CHCl.

  6. Kinetic and products study of the gas-phase reaction of Lewisite with ozone under atmospheric conditions.

    PubMed

    Wang, Haitao; Zhang, Yuanpeng; Guo, Xiaodi; Shao, Yusheng; Gao, Runli; Liang, Dejian; Sun, Hao

    2016-02-01

    The rate constant for the gas-phase reaction of O3 and Lewisite was studied in air using the smog chamber technique. The experiments were carried out under pseudo-first-order reaction conditions with [O3]≪[Lewisite]. The observed rate constant of O3 with Lewisite was (7.83 ± 0.38) × 10(-19)cm(3)/(molecule·sec) at 298 ± 2K. Lewisite was discussed in terms of reactivity with O3 and its relationship with the ionization potential. Our results show that the rate constant for the gas-phase reaction of O3 with Lewisite is in line with the trend of the rate constants of O3 with haloalkenes.

  7. Europa's Atmosphere: Production & Loss

    NASA Astrophysics Data System (ADS)

    Bagenal, F.; Cassidy, T. A.; Dols, V.; Crary, F. J.

    2013-12-01

    Europa is embedded not only in the ionized material of the Io plasma torus, but is also surrounded by the material (both ionized and neutral) produced by the interaction of this plasma with the moon's surface and atmosphere. Moreover, there are energetic ions and electrons that diffuse inwards from the outer magnetosphere and interact with the moon and surrounding neutral clouds. The multiple components of Europa's environment are thought to vary on timescales of hours to weeks and to be strongly coupled. Europa's O2 atmosphere is created by ion bombardment of the surface. Earlier studies assumed that the energetic (10s keV) ions were responsible (see review in Smyth and Marconi, 2006). New research (Cassidy et al. 2013) suggests that the 'thermal' ion population of the Io plasma torus produces most of Europa's O2. But this cooler population is easily diverted by currents induced in Europa's ionosphere and prevented from reaching the surface. This feedback has not been adequately explored. Modelers have historically focused on a single piece of the puzzle; plasma modelers assume a static atmosphere and atmosphere modelers assume static plasma. We are now in a position to consider these new sources of atmosphere and determine how the observed system comes about as well as quantify the timescales and causes of its evolution. This begs the question is Europa's atmosphere-magnetosphere interaction self-regulating? We are specifically interested in how the system responds to changes - for example, how does Europa's atmosphere change when the inflowing plasma flux increases or decreases? What is the corresponding change in the electrodynamics and diversion of plasma flow around Europa? How much and on what time scale does the extended neutral cloud respond? And what are the consequences for the influx of energetic particles? We model this coupled system to address how each component responds to changes in the other components.

  8. Atmospheric chemistry of perfluorocyclopentene (cyc-CF2CF2CF2CF=CF-): Kinetics, products and mechanism of gas-phase reactions with OH radicals, and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Zhang, Ni; Uchimaru, Tadafumi; Guo, Qin; Qing, Feiyao; Chen, Liang; Mizukado, Junji

    2017-07-01

    As a high-profile etching gas, perfluorocyclopentene (cyc-CF2CF2CF2CF=CF-) should be assessed for its atmospheric chemistry and environmental impact prior to expanding its industrial applications. However, the corresponding studies have been limited. In this study, the rate constants for the gas-phase reactions of cyc-CF2CF2CF2CF=CF- with OH radicals were determined by a relative rate method, and shown to be consistent with a theoretical computational results: k1-exp.(298 K) = (4.43 ± 0.10) × 10-14, k1-cal.(298 K) = 4.3 × 10-14, and k1-exp.(253-328 K) = (3.39 ± 0.86) × 10-13 exp(-(616 ± 78)/T) cm3 molecule-1 s-1. The atmospheric lifetime of cyc-CF2CF2CF2CF=CF- is 0.715 year, and its photochemical ozone creation potential is 0.48. Furthermore, the products and mechanism of the OH radical-initiated oxidation reactions were studied for the first time. The major products COF2, CO2, CO, and FC(O)OH are considered to have a negligible environmental effect. The radiative efficiency was determined as 0.246 W m-2 ppb-1, and the global warming potentials (GWPs) with 20-, 100-, and 500- year time horizon were estimated as 188, 51, and 15, respectively. The GWP100 value is significantly lower than those of the replacing targets (6630, 11100, 16 100, 23 500, and 9540 for CF4, C2F6, NF3, SF6, and c-C4F8, respectively).

  9. Europa's Atmosphere: Production & Loss

    NASA Astrophysics Data System (ADS)

    Bagenal, Fran; Cassidy, T.; Dols, V.; Crary, F.

    2013-10-01

    Europa is embedded not only in the ionized material of the Io plasma torus, but is also surrounded by the material (both ionized and neutral) produced by the interaction of this plasma with the moon’s surface and atmosphere - as illustrated in the schematic below. Moreover, there are energetic ions and electrons that diffuse inwards from the outer magnetosphere and interact with the moon and surrounding neutral clouds. The multiple components of Europa’s environment are thought to vary on timescales of hours to weeks and to be strongly coupled. Europa’s O2 atmosphere is created by ion bombardment of the surface. Earlier studies assumed that the energetic (10s keV) ions were responsible (see review in Smyth and Marconi, 2006). New research (Cassidy et al. 2013) suggests that the “thermal” ion population of the Io plasma torus produces most of Europa’s O2. But this cooler population is easily diverted by currents induced in Europa’s ionosphere and prevented from reaching the surface. This feedback has not been adequately explored. Modelers have historically focused on a single piece of the puzzle; plasma modelers assume a static atmosphere and atmosphere modelers assume static plasma. We are now in a position to consider these new sources of atmosphere and determine how the observed system comes about as well as quantify the timescales and causes of its evolution. This begs the question is Europa’s atmosphere-magnetosphere interaction self-regulating? We are specifically interested in how the system responds to changes - for example, how does Europa’s atmosphere change when the inflowing plasma flux increases or decreases? What is the corresponding change in the electrodynamics and diversion of plasma flow around Europa? How much and on what time scale does the extended neutral cloud respond? And what are the consequences for the influx of energetic particles? We model this coupled system to address how each component responds to changes in the

  10. Atmospheric chemistry: Laboratory studies of kinetics of important reactions

    NASA Astrophysics Data System (ADS)

    Smith, S. J.

    Experiments to measure the rate constants for some reactions of the atmospherically important nitrate radical (NO3) are described using the discharge-flow technique. The nitrate radical was monitored by optical absorption at lambda = 662 nm. The reactions of NO3 with some stable organic and inorganic substrates are reported. The temperature dependences of some of the rate constants were also determined (298 less than T less than 523 K). In most cases, computer simulation was used to extract the rate constant for the primary process because the time-dependent behavior of (NO3) was affected by secondary reactions of NO3 with products of the primary interaction. The Arrhenius parameter for the reactions of NO3 with CH3CH3, CH2CH2, CH3OH, CHCl3, and HCl were determined. The activation energies for the reactions studied between NO3 and some alkynes are presented along with the corresponding pre-exponential factors. Some reactions were studied at room temperature (298 plus or minus 2 K) only and the rate constants found (in units of cubic cm/molecule sec) are: buta-1,3-diene (1.8 x 10 (exp -13), isobutene (2.8 x 10 (exp -13), HBr (1.3 x 10 (exp -15) and hex-2-yne (3.0 x 10 (exp -14). Non-Arrhenius behavior was found in the reactions of NO3 with n-butane, isobutane and propene. The empirical variation of these rate constants with temperature is presented. The curvature of the Arrhenius plots is discussed in terms of (1) a temperature-dependent pre-exponential factor, and (2) the possibility that two competing channels, possessing differing activation energies, exist for each reaction. The atmospheric implications of these reactions are discussed with reference to the nighttime production of nitric acid and the importance of the these reactions as loss processes for NO3.

  11. Red-light initiated atmospheric reactions of vibrationally excited molecules.

    PubMed

    Vaida, V; Donaldson, D J

    2014-01-21

    We present a brief review of long wavelength, red-light initiated chemistry from excited vibrational levels of the ground electronic state of atmospheric trace species. When sunlight driven electronic state reactions are not effective, photochemical processes occurring by vibrational overtone excitation have been found to be important in reactions of oxidized atmospheric compounds (acids, alcohols and peroxides) prevalent in the Earth's atmosphere. This review focuses on the fundamental energetic, mechanistic and dynamical aspects of unimolecular reactions of vibrationally excited atmospheric species. We will discuss the relevance of these red light initiated reactions to address the discrepancies between atmospheric measurements and results of standard atmospheric models.

  12. Reaction rates of atmospheric gases with lithium(silicon) alloy

    SciTech Connect

    Searcy, J Q; Reinhardt, F W

    1980-12-01

    Reaction rates of small pellets of Li(Si) alloy with atmospheric gases were studied as a prerequisite to specifying how this alloy should be handled during the production of thermal batteries. The results indicate that Li(Si) reacts with oxygen and nitrogen at ambient conditions too slowly to be of concern, but it reacts very rapidly with water vapor. Rate expressions and constants are developed that allow calculating the weight gain of Li(Si) after its reaction with water vapor, and calculated values are given for three water-vapor concentrations that typify those used in dry rooms where thermal batteries are produced.

  13. Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants.

    PubMed

    Zhang, Yang; Shu, Jinian; Zhang, Yuanxun; Yang, Bo

    2013-09-01

    The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10-dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.

  14. Atmospheric science and power production

    SciTech Connect

    Randerson, D.

    1984-07-01

    This is the third in a series of scientific publications sponsored by the US Atomic Energy Commission and the two later organizations, the US Energy Research and Development Adminstration, and the US Department of Energy. The first book, Meteorology and Atomic Energy, was published in 1955; the second, in 1968. The present volume is designed to update and to expand upon many of the important concepts presented previously. However, the present edition draws heavily on recent contributions made by atmospheric science to the analysis of air quality and on results originating from research conducted and completed in the 1970s. Special emphasis is placed on how atmospheric science can contribute to solving problems relating to the fate of combustion products released into the atmosphere. The framework of this book is built around the concept of air-quality modeling. Fundamentals are addressed first to equip the reader with basic background information and to focus on available meteorological instrumentation and to emphasize the importance of data management procedures. Atmospheric physics and field experiments are described in detail to provide an overview of atmospheric boundary layer processes, of how air flows around obstacles, and of the mechanism of plume rise. Atmospheric chemistry and removal processes are also detailed to provide fundamental knowledge on how gases and particulate matter can be transformed while in the atmosphere and how they can be removed from the atmosphere. The book closes with a review of how air-quality models are being applied to solve a wide variety of problems. Separate analytics have been prepared for each chapter.

  15. Reaction product imaging

    SciTech Connect

    Chandler, D.W.

    1993-12-01

    Over the past few years the author has investigated the photochemistry of small molecules using the photofragment imaging technique. Bond energies, spectroscopy of radicals, dissociation dynamics and branching ratios are examples of information obtained by this technique. Along with extending the technique to the study of bimolecular reactions, efforts to make the technique as quantitative as possible have been the focus of the research effort. To this end, the author has measured the bond energy of the C-H bond in acetylene, branching ratios in the dissociation of HI, the energetics of CH{sub 3}Br, CD{sub 3}Br, C{sub 2}H{sub 5}Br and C{sub 2}H{sub 5}OBr dissociation, and the alignment of the CD{sub 3} fragment from CD{sub 3}I photolysis. In an effort to extend the technique to bimolecular reactions the author has studied the reaction of H with HI and the isotopic exchange reaction between H and D{sub 2}.

  16. Heterogeneous atmospheric reactions - Sulfuric acid aerosols as tropospheric sinks

    NASA Technical Reports Server (NTRS)

    Baldwin, A. C.; Golden, D. M.

    1979-01-01

    The reaction probabilities of various atmospheric species incident on a bulk sulfuric acid surface are measured in order to determine the role of sulfuric acid aerosols as pollutant sinks. Reaction products and unreacted starting materials leaving a Knudsen cell flow reactor after collision at 300 K with a H2SO4 surface or a soot surface were detected by mass spectrometry. Significant collision reaction probabilities are observed on a H2SO4 surface for H2O2, HNO3, HO2NO2, ClONO2, N2O5, H2O and NH3, and on soot for NH3. Estimates of the contribution of heterogeneous reactions to pollutant removal under atmospheric conditions indicate that while aerosol removal in the stratosphere is insignificant (loss rate constants approximately 10 to the -10th/sec), heterogeneous reactions may be the dominant loss process for several tropospheric species (loss rate constant approximately 10 to the -5th/sec, comparable to photolysis rate constants).

  17. Crossed molecular beam studies of atmospheric chemical reaction dynamics

    SciTech Connect

    Zhang, Jingsong

    1993-04-01

    The dynamics of several elementary chemical reactions that are important in atmospheric chemistry are investigated. The reactive scattering of ground state chlorine or bromine atoms with ozone molecules and ground state chlorine atoms with nitrogen dioxide molecules is studied using a crossed molecular beams apparatus with a rotatable mass spectrometer detector. The Cl + O3 → ClO + O2 reaction has been studied at four collision energies ranging from 6 kcal/mole to 32 kcal/mole. The derived product center-of-mass angular and translational energy distributions show that the reaction has a direct reaction mechanism and that there is a strong repulsion on the exit channel. The ClO product is sideways and forward scattered with respect to the Cl atom, and the translational energy release is large. The Cl atom is most likely to attack the terminal oxygen atom of the ozone molecule. The Br + O3 → ClO + O2 reaction has been studied at five collision energies ranging from 5 kcal/mole to 26 kcal/mole. The derived product center-of-mass angular and translational energy distributions are quite similar to those in the Cl + O3 reaction. The Br + O3 reaction has a direct reaction mechanism similar to that of the Cl + O3 reaction. The electronic structure of the ozone molecule seems to play the central role in determining the reaction mechanism in atomic radical reactions with the ozone molecule. The Cl + NO2 → ClO + NO reaction has been studied at three collision energies ranging from 10.6 kcal/mole to 22.4 kcal/mole. The center-of-mass angular distribution has some forward-backward symmetry, and the product translational energy release is quite large. The reaction proceeds through a short-lived complex whose lifetime is less than one rotational period. The experimental results seem to show that the Cl atom mainly attacks the oxygen atom instead of the nitrogen atom of the NO2

  18. Possible atmospheric lifetimes and chemical reaction mechanisms for selected HCFCs, HFCs, CH3CCl3, and their degradation products against dissolution and/or degradation in seawater and cloudwater

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Chameides, W. L.

    1990-01-01

    For a wide variety of atmospheric species including CO2, HNO3, and SO2, dissolution in seawater or cloudwater followed by hydrolysis or chemical reaction represents a primary pathway for removal from the atmosphere. In order to determine if this mechanism can also remove significant amounts of atmospheric chlorofluorocarbons (HCFC's), fluorocarbons (HFC's), and their degradation products, an investigation was undertaken as part of the Alternative Fluorocarbons Environmental Acceptability Study (AFEAS). In this investigation, the rates at which CHCl2CF3 (HCFC-123), CCl2FCH3 (HCFC-141b), CClF2CH3 (HCFC-142b), CHClF2 (HCFC-22), CHClFCF3 (HCFC-124) CH2FCF3 (HFC-134a) CHF2CH3 (HFC-152a), CHF2CF3 (HFC-125), and CH3CCl3 can be dissolved in the oceans and in cloudwater were estimated from the species' thermodynamic and chemical properties using simple mathematical formulations to simulate the transfer of gases from the atmosphere to the ocean or cloudwater. The ability of cloudwater and rainwater to remove gas phase degradation products of these compounds was also considered as was the aqueous phase chemistry of the degradation products. The results of this investigation are described.

  19. A laboratory flow reactor with gas particle separation and on-line MS/MS for product identification in atmospherically important reactions

    NASA Astrophysics Data System (ADS)

    Bennett, J. F.; Collin, F.; Hastie, D. R.

    2009-12-01

    A system to study the gas and particle phase products from gas phase hydrocarbon oxidation is described. It consists of a gas phase photochemical flow reactor followed by a diffusion membrane denuder to remove gases from the reacted products, or a filter to remove the particles. Chemical analysis is performed by an atmospheric pressure chemical ionization (APCI) triple quadrupole mass spectrometer. A diffusion membrane denuder is shown to remove trace gases to below detectable limits so the particle phase can be studied. The system was tested by examining the products of the oxidation of m-xylene initiated by HO radicals. Dimethylphenol was observed in both the gas and particle phases although individual isomers could not be identified. Two furanone isomers, 5-methyl-2(3H)furanone and 3-methyl-2(5H)furanone were identified in the particulate phase, but the isobaric product 2,5 furandione was not observed. One isomer of dimethyl-nitrophenol was identified in the particle phase but not in the gas phase.

  20. A Computational Study of Acid Catalyzed Aerosol Reactions of Atmospherically Relevant Epoxides

    EPA Science Inventory

    Epoxides are important intermediates of atmospheric isoprene oxidation. Their subsequent reactions in the particle phase lead to the production of organic compounds detected in ambient aerosols. We apply density functional theory to determine the important kinetic factors that ...

  1. A Computational Study of Acid Catalyzed Aerosol Reactions of Atmospherically Relevant Epoxides

    EPA Science Inventory

    Epoxides are important intermediates of atmospheric isoprene oxidation. Their subsequent reactions in the particle phase lead to the production of organic compounds detected in ambient aerosols. We apply density functional theory to determine the important kinetic factors that ...

  2. Effect of temperature oscillation on chemical reaction rates in the atmosphere

    NASA Technical Reports Server (NTRS)

    Eberstein, I. J.

    1974-01-01

    The effect of temperature fluctuations on atmospheric ozone chemistry is examined by considering the Chapman photochemical theory of ozone transport to calculate globally averaged ozone production rates from mean reaction rates, activation energies, and recombination processes.

  3. Products of the reaction between alpha- or gamma-tocopherol and nitrogen oxides analyzed by high-performance liquid chromatography with UV-visible and atmospheric pressure chemical ionization mass spectrometric detection.

    PubMed

    Nagata, Yoshiko; Matsumoto, Yohta; Kanazawa, Hideko

    2004-05-21

    The reaction products of alpha- or gamma-tocopherol with nitric oxide in the presence of molecular oxygen were isolated and characterized. The consumption of tocopherols and the formation of the major products were monitored by high-performance liquid chromatography (HPLC) by a gradient elution method. The quantitative analysis of these compounds with UV-Vis detectors, however, was interfered by several minor products having similar UV spectra and retention times as those of the major ones. In order to establish a quantitative analytical method for the products, we investigated other detection methods, and found that atmospheric pressure chemical ionization (APCI), LC-MS was a more selective and better analytical method for these compounds.

  4. Kinetics and product identification of the reactions of (E)-2-hexenyl acetate and 4-methyl-3-penten-2-one with OH radicals and Cl atoms at 298 K and atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Gaona-Colmán, Elizabeth; Blanco, María B.; Teruel, Mariano A.

    2017-07-01

    Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with two biogenic volatile organic compounds as (E)-2-hexenyl acetate and 4-methyl-3-penten-2-one have been determined at 298 K and atmospheric pressure. The decay of the organics was followed using a chromatograph with a flame ionization detector (GC-FID) and the rate constants were determined using a relative rate method. Rate coefficients are found to be (in cm3 molecule-1 s-1): k1(OH + (E)-2-hexenyl acetate) = (6.88 ± 1.41) × 10-11, k2(Cl + (E)-2-hexenyl acetate) = (3.10 ± 1.13) × 10-10, k3(OH + 4-methyl-3-penten-2-one) = (1.02 ± 0.20) × 10-10 and k4(Cl + 4-methyl-3-penten-2-one) = (2.66 ± 0.90) × 10-10 at 298 K. This is the first kinetic experimental study for these reactions studied under atmospheric pressure. The rate coefficients are compared with previous determinations for other unsaturated and oxygenated compounds and reactivity trends are presented. Products identification studies were performed using solid-phase microextraction (SPME) method employing on-fiber products derivatization with o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride using gas chromatograph with a mass spectrometer detector (GC-MS) for the reactions studied. In addition, atmospheric lifetimes of the unsaturated compounds studied are estimated and compared with other tropospheric sinks for these compounds.

  5. Atmospheric pressure microwave assisted heterogeneous catalytic reactions.

    PubMed

    Chemat-Djenni, Zoubida; Hamada, Boudjema; Chemat, Farid

    2007-07-11

    The purpose of the study was to investigate microwave selective heating phenomena and their impact on heterogeneous chemical reactions. We also present a tool which will help microwave chemists to answer to such questions as "My reaction yields 90% after 7 days at reflux; is it possible to obtain the same yield after a few minutes under microwaves?" and to have an approximation of their reactions when conducted under microwaves with different heterogeneous procedures. This model predicting reaction kinetics and yields under microwave heating is based on the Arrhenius equation, in agreement with experimental data and procedures.

  6. Kinetics of chlorine atom reactions with molecules of atmospheric interest

    NASA Astrophysics Data System (ADS)

    Goliff, Wendy Suzanne

    1997-07-01

    The major factor in determining whether chlorine atom (Cl) reactions are important sinks in the stratosphere for hydrogen-containing species is the relative rate constants for attack by Cl versus attack by hydroxyl (HO). Although the rates of HO with methyl bromide (CH3Br), HFC-32 (CH2F2), HFC-125 (CHF2CF3), HFC-152a (CH3CHF2), HCFC-123 (CHCl2CF3) and HCFC-124 (CHClFCF3) are well-known, few data are available for their rate constants with Cl. The thermal reaction rate constants of hydrogen abstraction by Cl with CH3Br, CH2F2,/ CHF2CF3,/ CH3CHF2,/ CHCl2CF3/ and/ CHClFCF3 in the gas phase have been measured at 298K and 4,000 torr. 38Cl was reacted with each species against the common competitor, bromotrifluoroethylene (CF2=CFBr). The decomposition product of the competitor reaction, 38-chlorotrifluoroethylene (CF2[=]CF38Cl), was measured by radiogas chromatography. The relative rate constants were converted to an absolute scale by comparison to the well- known rate constant of Cl with methane (CH4). The gas phase substitution reactions of thermal atomic chlorine with methyl iodide and methyl bromide to form methyl chloride have been Cl+CH3X/to CH3Cl+X/ (X=Br,I)investigated at two pressures (4,000 torr & 760 torr) and three temperatures (273K, 295K, 343K), using radioactive 38Cl from the thermal neutron induced 37Cl(n,/gamma)38Cl nuclear reaction. The initially energetic 38Cl atoms are thermalized by inelastic collisions with inert CClF3 prior to reaction with the methyl halide. The yields of CH338Cl were analyzed by radiogas chromatography. The yields of CH338Cl from thermal chlorine atom reactions at 295K are 8.6% from methyl iodide, and 0.5% from methyl bromide. The corresponding reaction rate constant for thermal chlorine attack to form CH3Cl at 295K is (1.7/pm0.2)×10-15/ cm3 molecule- 1/sec-1 with CH3Br. The substitution reaction with methyl iodide is pressure-independent over the 1-5 atmosphere range. The yields of CH338Cl increase with decreasing temperature

  7. Mineral Reaction Buffering of Venus' Atmosphere: Constraints for Terrestrial Exoplanets

    NASA Astrophysics Data System (ADS)

    Treiman, A. H.; Bullock, M. A.

    2011-12-01

    For many years, it has been suggested that the composition of Venus' atmosphere, notably its abundance of CO2, is controlled by gas-solid reactions at its surface. However, the suggested reaction for Venus atmosphere, CaCO3 + SiO2 = CaSiO3 + CO2, cannot act as a buffer - the pressure-temperature trajectory of the reaction and that of the atmosphere (a dry adiabat) do not provide buffering capacity. Instead, perturbations to T or P(CO2) would produce catastrophic expansion or collapse of the atmosphere. This instability can be generalized to all devolatilization reactions that produce a radiatively active gas in a planetary atmosphere dominated by such gases, and gives a simple thermochemical criterion for whether a reaction could buffer such an atmosphere. Simple decarbonation reactions fail this criterion, implying that the abundance of CO2 in a CO2-dominated atmosphere cannot be buffered by chemical reactions with the surface. The same inference holds for the abundance of H2O in an H2O-dominated (steam) atmosphere (e.g., exoplanet GJ 1214b), and for the abundance of methane above a methane-hydrate ice surface (e.g., a Titan-like exoplanet). Buffering of minor gases is more likely; the proposed mineral buffer reaction for SO2 in the Venus atmosphere (FeS2 + CO2 = Fe3O4 + SO2 + CO) passes the thermochemical criterion, as does a reaction involving Ca sulfate (CaSO4 + CO = CaCO3 + SO2). These inferences can be generalized to extrasolar Venus-like planets - those with surfaces hot enough to permit rapid chemical reactions between solids and gas, yet cool enough that their atmospheres contain (are dominated by) gases active in thermal radiative equilibria. On the other hand, it seems likely that abundances of minor atmospheric gas species can be buffered by crust-atmosphere chemical reactions. So, minor species in exoplanet atmospheres may be particularly important for constraining the chemical characteristics of their surfaces.

  8. Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implication for PM2.5

    NASA Astrophysics Data System (ADS)

    Jaoui, M.; Lewandowski, M.; Docherty, K.; Offenberg, J. H.; Kleindienst, T. E.

    2014-06-01

    Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H2O2 or NOx. Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The chemical composition of the gas phase and SOA was analyzed using derivative-based methods (BSTFA, BSTFA + PFBHA, or DNPH) followed by gas chromatography-mass spectrometry (GC-MS) or high-performance liquid chromatography (HPLC) analysis of the derivative compounds. The analysis showed the occurrence of more than 60 oxygenated organic compounds in the gas and particle phases, of which 31 organic monomers were tentatively identified. The major identified products include glyceric acid, d-threitol, erythritol, d-threonic acid, meso-threonic acid, erythrose, malic acid, tartaric acid, and carbonyls including glycolaldehyde, glyoxal, acrolein, malonaldehyde, glyceraldehyde, and peroxyacryloyl nitrate (APAN). Some of these were detected in ambient PM2.5 samples and could potentially serve as organic markers of 1,3-butadiene (13BD). Furthermore, a series of oligoesters were detected and found to be produced from esterification reactions among compounds bearing alcoholic groups and compounds bearing acidic groups. Time profiles are provided for selected compounds. SOA was analyzed for organic mass to organic carbon (OM / OC) ratio, effective enthalpy of vaporization (ΔHvapeff), and aerosol yield. The average OM / OC ratio and SOA density were 2.7 ± 0.09 and 1.2 ± 0.05, respectively. The average ΔHvapeff was 26.1 ± 1.5 kJ mol-1, a value lower than that of isoprene SOA. The average laboratory SOA yield measured in this study at aerosol mass concentrations between 22.5 and 140.2 μg m-3 was 0.025 ± 0.011, a value consistent with the literature (0.021-0.178). While the focus of this study has been examination of the particle-phase measurements, the gas

  9. Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implications for PM2.5

    NASA Astrophysics Data System (ADS)

    Jaoui, M.; Lewandowski, M.; Docherty, K.; Offenberg, J. H.; Kleindienst, T. E.

    2014-12-01

    Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H2O2 or NOx. Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The chemical composition of the gas phase and SOA was analyzed using derivative-based methods (BSTFA, BSTFA + PFBHA, or DNPH) followed by gas chromatography-mass spectrometry (GC-MS) or high-performance liquid chromatography (HPLC) analysis of the derivative compounds. The analysis showed the occurrence of more than 60 oxygenated organic compounds in the gas and particle phases, of which 31 organic monomers were tentatively identified. The major identified products include glyceric acid, d-threitol, erythritol, d-threonic acid, meso-threonic acid, erythrose, malic acid, tartaric acid, and carbonyls including glycolaldehyde, glyoxal, acrolein, malonaldehyde, glyceraldehyde, and peroxyacryloyl nitrate (APAN). Some of these were detected in ambient PM2.5 samples, and could potentially serve as organic markers of 13BD. Furthermore, a series of oligoesters were detected and found to be produced through chemical reactions occurring in the aerosol phase between compounds bearing alcoholic groups and compounds bearing acidic groups. SOA was analyzed for organic mass to organic carbon (OM /OC) ratio, effective enthalpy of vaporization (Δ Hvapeff), and aerosol yield. The average OM /OC ratio and SOA density were 2.7 ± 0.09 and 1.2 ± 0.05, respectively. The average Δ Hvapeff was -26.08 ± 1.46 kJ mol-1, a value lower than that of isoprene SOA. The average laboratory SOA yield measured in this study at aerosol mass concentrations between 22.5 and 140.2 μg m-3 was 0.025 ± 0.011, a value consistent with the literature (0.021-0.178). While the focus of this study has been examination of the particle-phase measurements, the gas-phase photooxidation products have also been

  10. Real-time air monitoring of mustard gas and Lewisite 1 by detecting their in-line reaction products by atmospheric pressure chemical ionization ion trap tandem mass spectrometry with counterflow ion introduction.

    PubMed

    Okumura, Akihiko; Takada, Yasuaki; Watanabe, Susumu; Hashimoto, Hiroaki; Ezawa, Naoya; Seto, Yasuo; Sekiguchi, Hiroshi; Maruko, Hisashi; Takayama, Yasuo; Sekioka, Ryoji; Yamaguchi, Shintaro; Kishi, Shintaro; Satoh, Takafumi; Kondo, Tomohide; Nagashima, Hisayuki; Nagoya, Tomoki

    2015-01-20

    A new method enabling sensitive real-time air monitoring of highly reactive chemical warfare agents, namely, mustard gas (HD) and Lewisite 1 (L1), by detecting ions of their in-line reaction products instead of intact agents, is proposed. The method is based on corona discharge-initiated atmospheric pressure chemical ionization coupled with ion trap tandem mass spectrometry (MS(n)) via counterflow ion introduction. Therefore, it allows for highly sensitive and specific real-time detection of a broad range of airborne compounds. In-line chemical reactions, ionization reactions, and ion fragmentations of these agents were investigated. Mustard gas is oxygenated in small quantity by reactive oxygen species generated in the corona discharge. With increasing air humidity, the MS(2) signal intensity of protonated molecules of mono-oxygenated HD decreases but exceeds that of dominantly existing intact HD. This result can be explained in view of proton affinity. Lewisite 1 is hydrolyzed and oxidized. As the humidity increases from zero, the signal of the final product, namely, didechlorinated, dihydroxylated, and mono-oxygenated L1, quickly increases and reaches a plateau, giving the highest MS(2) and MS(3) signals among those of L1 and its reaction products. The addition of minimal moisture gives the highest signal intensity, even under low humidity. The method was demonstrated to provide sufficient analytical performance to meet the requirements concerning hygienic management and counter-terrorism. It will be the first practical method, in view of sensitivity and specificity, for real-time air monitoring of HD and L1 without sample pretreatment.

  11. A Flexible Transition State Searching Method for Atmospheric Reaction Systems

    SciTech Connect

    Lin, Xiao-Xiao; Liu, Yi-Rong; Huang, Teng; Chen, Jiao; Jiang, Shuai; Huang, Wei

    2015-04-01

    The precise and rapid exploration of transition states (TSs) is a major challenge when studying atmospheric reactions due to their complexity. In this work, a Monte Carlo Transition State Search Method (MCTSSM), which integrates Monte Carlo sampling technique with transition state optimization methods using an efficient computer script, has been developed for transition state searches. The efficiency and the potential application in atmospheric reactions of this method have been demonstrated by three types of test suits related to the reactions of atmospheric volatile organic compounds (VOCs): (1) OH addition, (2) OH hydrogen-abstraction, and (3) the other reactive group (e.g. Cl, O3, NO3), especially for the reaction of β-pinene-sCI (stabilized Criegee Intermediates) with water. It was shown that the application of this method with effective restricted parameters has greatly simplified the time-consuming and tedious manual search procedure for transition state (TS) of the bimolecular reaction systems.

  12. A flexible transition state searching method for atmospheric reaction systems

    NASA Astrophysics Data System (ADS)

    Lin, Xiao-Xiao; Liu, Yi-Rong; Huang, Teng; Chen, Jiao; Jiang, Shuai; Huang, Wei

    2015-04-01

    The precise and rapid exploration of transition states (TSs) is a major challenge when studying atmospheric reactions due to their complexity. In this work, a Monte Carlo Transition State Search Method (MCTSSM), which integrates Monte Carlo sampling technique with transition state optimization methods using an efficient computer script, has been developed for transition state searches. The efficiency and the potential application in atmospheric reactions of this method have been demonstrated by three types of test suits related to the reactions of atmospheric volatile organic compounds (VOCs): (1) OH addition, (2) OH hydrogen-abstraction, and (3) the other reactive group (e.g. Cl, O3, NO3), especially for the reaction of β-pinene-sCI (stabilized Criegee Intermediates) with water. It was shown that the application of this method with effective restricted parameters has greatly simplified the time-consuming and tedious manual search procedure for transition state (TS) of the bimolecular reaction systems.

  13. Atmospheric Chemistry: Laboratory Studies of Kinetics of Important Reactions.

    NASA Astrophysics Data System (ADS)

    Smith, S. J.

    Available from UMI in association with The British Library. Requires signed TDF. This thesis describes the experiments to measure the rate constants for some reactions of the atmospherically important nitrate radical (NO_3) using the discharge-flow technique. The nitrate radical was monitored by optical absorption at lambda = 662 nm. The reactions of NO_3 with some stable organic and inorganic substrates are reported. The temperature dependences of some of the rate constants have also been determined (298 < T < 523 K). In most cases, computer simulation was used to extract the rate constant for the primary process because the time-dependent behaviour of (NO_3) was affected by secondary reactions of NO_3 with products of the primary interaction. The Arrhenius parameter in parentheses (E _{rm a}/kJ mol^ {-1}, A/cm^3 molecule ^{-1}s^ {-1} respectively) for the following reactions have been determined: ethane (37, 6.7 times 10^{-12}), ethylene (25.8, 6.3 times 10^ {-12}), CH_3OH (21.3, 1.2 times 10^ {-12}), CHCiota_3 (23.4, 8.6 times 10 ^{-13}) and HCl (27.7, 4 times 10^{-12}). The activation energies for the reactions studied between NO_3 and some alkynes are represented well by the value 25 +/- 3 kJ mol^{-1} and the corresponding pre-exponential factors (expressed as ln(10 ^{13}A/cm^3 molecule^{-1}s ^{-1}) are as follows: C_2H_2 (1.6 +/- 1.4), C_3H _4 (5.0 +/- 1.4), 1-C_4H_6 (5.8 +/- 1.0), 1-C_5 H_8 (5.7 +/- 0.6) and 1-C_6H _{10} (4.5 +/- 0.4). Some reactions were studied at room temperature _3(298 +/- 2 K) only and the rate constants found (in units of cm ^3 molecule^{ -1}s^{-1}) are: buta-1,3-diene (1.8 times 10 ^{-13}), isobutene (2.8 times 10^{-13 }), HBr (1.3 times 10 ^{-15}) and hex-2-yne (3.0 times 10^{-14 }). Non-Arrhenius behaviour was found in the reactions of NO_3 with n-butane, isobutane and propene. The empirical variation of these rate constants with temperature is well represented by the three parameter expressions:. k(T) = 1.2 times 10 ^{-46}T^{11

  14. The affects on Titan atmospheric modeling by variable molecular reaction rates

    NASA Astrophysics Data System (ADS)

    Hamel, Mark D.

    The main effort of this thesis is to study the production and loss of molecular ions in the ionosphere of Saturn's largest moon Titan. Titan's atmosphere is subject to complex photochemical processes that can lead to the production of higher order hydrocarbons and nitriles. Ion-molecule chemistry plays an important role in this process but remains poorly understood. In particular, current models that simulate the photochemistry of Titan's atmosphere overpredict the abundance of the ionosphere's main ions suggesting a flaw in the modeling process. The objective of this thesis is to determine which reactions are most important for production and loss of the two primary ions, C2H5+ and HCNH+, and what is the impact of uncertainty in the reaction rates on the production and loss of these ions. In reviewing the literature, there is a contention about what reactions are really necessary to illuminate what is occurring in the atmosphere. Approximately seven hundred reactions are included in the model used in this discussion (INT16). This paper studies what reactions are fundamental to the atmospheric processes in Titan's upper atmosphere, and also to the reactions that occur in the lower bounds of the ionosphere which are used to set a baseline molecular density for all species, and reflects what is expected at those altitudes on Titan. This research was conducted through evaluating reaction rates and cross sections available in the scientific literature and through conducting model simulations of the photochemistry in Titan's atmosphere under a range of conditions constrained by the literature source. The objective of this study is to determine the dependence of ion densities of C2H5+ and HCNH+ on the uncertainty in the reaction rates that involve these two ions in Titan's atmosphere.

  15. Heterogeneous reactions important in atmospheric ozone depletion: a theoretical perspective.

    PubMed

    Bianco, Roberto; Hynes, James T

    2006-02-01

    Theoretical studies of the mechanisms of several heterogeneous reactions involving ClONO(2), H(2)O, HCl, HBr, and H(2)SO(4) important in atmospheric ozone depletion are described, focused primarily on reactions on aqueous aerosol surfaces. Among the insights obtained is the active chemical participation of the surface water molecules in several of these reactions. The general methodology adopted allows reduction of these complex chemical problems to meaningful model systems amenable to quantum chemical calculations.

  16. Reaction products of chlorine dioxide.

    PubMed Central

    Stevens, A A

    1982-01-01

    Inspection of the available literature reveals that a detailed investigation of the aqueous organic chemistry of chlorine dioxide and systematic identification of products formed during water disinfection has not been considered. This must be done before an informed assessment can be made of the relative safety of using chlorine dioxide as a disinfectant alternative to chlorine. Although trihalomethanes are generally not formed by the action of chlorine dioxide, the products of chlorine dioxide treatment of organic materials are oxidized species, some of which also contain chlorine. The relative amounts of species types may depend on the amount of chlorine dioxide residual maintained and the concentration and nature of the organic material present in the source water. The trend toward lower concentrations of chlorinated by-products with increasing ClO2 concentration, which was observed with phenols, has not been observed with natural humic materials as measured by the organic halogen parameter. Organic halogen concentrations have been shown to increase with increasing chlorine dioxide dose, but are much lower than those observed when chlorine is applied. Aldehydes have been detected as apparent by-products of chlorine dioxide oxidation reactions in a surface water that is a drinking water source. Some other nonchlorinated products of chlorine dioxide treatment may be quinones and epoxides. The extent of formation of these moieties within the macromolecular humic structure is also still unknown. PMID:7151750

  17. Role of Double Hydrogen Atom Transfer Reactions in Atmospheric Chemistry.

    PubMed

    Kumar, Manoj; Sinha, Amitabha; Francisco, Joseph S

    2016-05-17

    Hydrogen atom transfer (HAT) reactions are ubiquitous and play a crucial role in chemistries occurring in the atmosphere, biology, and industry. In the atmosphere, the most common and traditional HAT reaction is that associated with the OH radical abstracting a hydrogen atom from the plethora of organic molecules in the troposphere via R-H + OH → R + H2O. This reaction motif involves a single hydrogen transfer. More recently, in the literature, there is an emerging framework for a new class of HAT reactions that involves double hydrogen transfers. These reactions are broadly classified into four categories: (i) addition, (ii) elimination, (iii) substitution, and (iv) rearrangement. Hydration and dehydration are classic examples of addition and elimination reactions, respectively whereas tautomerization or isomerization belongs to a class of rearrangement reactions. Atmospheric acids and water typically mediate these reactions. Organic and inorganic acids are present in appreciable levels in the atmosphere and are capable of facilitating two-point hydrogen bonding interactions with oxygenates possessing an hydroxyl and/or carbonyl-type functionality. As a result, acids influence the reactivity of oxygenates and, thus, the energetics and kinetics of their HAT-based chemistries. The steric and electronic effects of acids play an important role in determining the efficacy of acid catalysis. Acids that reduce the steric strain of 1:1 substrate···acid complex are generally better catalysts. Among a family of monocarboxylic acids, the electronic effects become important; barrier to the catalyzed reaction correlates strongly with the pKa of the acid. Under acid catalysis, the hydration of carbonyl compounds leads to the barrierless formation of diols, which can serve as seed particles for atmospheric aerosol growth. The hydration of sulfur trioxide, which is the principle mechanism for atmospheric sulfuric acid formation, also becomes barrierless under acid catalysis

  18. Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations.

    PubMed

    Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B

    2011-01-20

    Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF

  19. Reactions of Cl atoms with alkyl esters: kinetic, mechanism and atmospheric implications.

    PubMed

    Ifang, Stefanie; Benter, Thorsten; Barnes, Ian

    2015-04-01

    Rate coefficients have been measured for the reaction of Cl atoms with a series of alkyl esters at 298 ± 2 K and atmospheric pressure in a large volume photoreactor using the relative kinetic technique. The kinetic data have been used in conjunction with other literature studies on the reactions of Cl atoms with esters to revise the existing values for ester substituent factors in a structure activity relationship (SAR) for Cl reactions. Product studies are reported for the reactions of Cl atoms with isopropyl ethanoate and methyl-2-methyl-propanoate under NO x -free conditions. These studies highlight the types of products that can be expected when oxidation occurs at R groups on the acyl (-C(O)OR) and oxy (RC(O)O-) sides of the ester functionality where R is a straight or branched chain alkyl entity. Possible atmospheric repercussions of the atmospheric chemistry of esters are considered.

  20. Immediate reactions to rubber products.

    PubMed

    Fuchs, T; Wahl, R

    1992-01-01

    There is an increasing incidence of contact urticaria (CU) and systemic reactions to rubber products. Thirty-one patients are presented: most were atopic (20/31) and women (26/31); 71% worked in the medical field; 32.2% (10/31) showed signs of hand dermatitis. In 28 patients (90.3%), rub and/or prick tests with liquid latex in different dilutions and with latex gloves led to an immediate type of positive reaction. The allergen(s) appear in part to be water soluble: 20 of 28 patients (71.4%) revealed positive test reactions to an aqueous glove extract. In two patients, urticarial test reactions to tetramethylthiuram disulfide (TMTD), mercapto mix, and p-phenylenediamine (PPD mix) were considered as possible contributing factors of CU. Cornstarch was negative in all patients (scratch). Sixteen of 27 sera (59.2%) showed radioallergosorbent (RAST) class 0 using latex allergen disks. Sodium dodecyl sulfate-polyacoyl-amide (SDS-PAGE) determined protein bands of less than or equal to 14 kD (not allergen specific) and approx 28 kD. The Western blot detected the 28 kD protein as allergen in the sera of three patients. Isoelectric focusing (IEF) proved no protein bands. Immunoprinting performed with sera of five patients presented allergen bands in a pH range between 3.8 and 4.55. This shows the radio staining (immunoprint) is more sensitive than is the Coomassie blue staining. Although three sera showed RAST class 0, immunoblotting detected allergen bands. In this case the immunoblot appears to be more sensitive than the RAST. A cross reactivity between latex and banana could not be established. Alternative gloves are Neolon (neoprene) or Elastyren (styrene-butadiene polymer).

  1. Reaction Profiles and Molecular Dynamics Simulations of Cyanide Radical Reactions Relevant to Titan's Atmosphere

    NASA Astrophysics Data System (ADS)

    Trinidad Pérez-Rivera, Danilo; Romani, Paul N.; Lopez-Encarnacion, Juan Manuel

    2016-10-01

    Titan's atmosphere is arguably the atmosphere of greatest interest that we have an abundance of data for from both ground based and spacecraft observations. As we have learned more about Titan's atmospheric composition, the presence of pre-biotic molecules in its atmosphere has generated more and more fascination about the photochemical process and pathways it its atmosphere. Our computational laboratory has been extensively working throughout the past year characterizing nitrile synthesis reactions, making significant progress on the energetics and dynamics of the reactions of .CN with the hydrocarbons acetylene (C2H2), propylene (CH3CCH), and benzene (C6H6), developing a clear picture of the mechanistic aspects through which these three reactions proceed. Specifically, first principles calculations of the reaction profiles and molecular dynamics studies for gas-phase reactions of .CN and C2H2, .CN and CH3CCH, and .CN and C6H6 have been carried out. A very accurate determination of potential energy surfaces of these reactions will allow us to compute the reaction rates which are indispensable for photochemical modeling of Titan's atmosphere.The work at University of Puerto Rico at Cayey was supported by Puerto Rico NASA EPSCoR IDEAS-ER program (2015-2016) and DTPR was sponsored by the Puerto Rico NASA Space Grant Consortium Fellowship. *E-mail: juan.lopez15@upr.edu

  2. A theoretical study of the atmospherically important radical-radical reaction BrO + HO2; the product channel O2(a(1)Δg) + HOBr is formed with the highest rate.

    PubMed

    Chow, Ronald; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2016-11-09

    A theoretical study has been made of the BrO + HO2 reaction, a radical-radical reaction which contributes to ozone depletion in the atmosphere via production of HOBr. Reaction enthalpies, activation energies and mechanisms have been determined for five reaction channels. Also rate coefficients have been calculated, in the atmospherically important temperature range 200-400 K, for the two channels with the lowest activation energies, both of which produce HOBr: (R1a) HOBr(X(1)A') + O2(X(3)Σ) and (R1b) HOBr(X(1)A') + O2(a(1)Δg). The other channels considered are: (R2) BrO + HO2 → HBr + O3, (R3) BrO + HO2 → OBrO + OH and (R4) BrO + HO2 → BrOO + OH. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/AVDZ level, while relative energies of the stationary points on the reaction surface were improved at a higher level (BD(TQ)/CBS or CCSD(T)/CBS). The computed standard reaction enthalpies (ΔH) for channels (R1a), (R1b), (R2), (R3) and (R4) are -47.5, -25.0, -4.3, 14.9 and 5.9 kcal mol(-1), and the corresponding computed activation energies (ΔE) are 2.53, -3.07, 11.83, 35.0 and 37.81 kcal mol(-1). These values differ significantly from those obtained in earlier work by Kaltsoyannis and Rowley (Phys. Chem. Chem. Phys., 2002, 4, 419-427), particularly for channel (R1b), and reasons for this are discussed. In particular, the importance of obtaining an open-shell singlet wavefunction, rather than a closed-shell singlet wavefunction, for the transition state of this channel is emphasized. Rate coefficient calculations from computed potential energy surfaces were made for BrO + HO2 for the first time. Although channel (R1a) is the most exothermic, channel (R1b) has the lowest barrier height, which is negative (at -3.07 kcal mol(-1)). Most rate coefficient calculations were therefore made for (R1b). A two transition state model has been used, involving an outer and an inner transition state. The inner transition state was

  3. Atmospheric chemistry of toxic contaminants. 1. Reaction rates and atmospheric persistence

    SciTech Connect

    Grosjean, D. )

    1990-10-01

    Using structure-reactivity relationships between reaction rate constants and ionization potentials for structural homologues, estimates are presented for the rate constants of the reactions of ozone, the hydroxyl radical, and the nitrate radical with forty toxic air contaminants for which no or little data are available. These rate constants are in turn used to estimate the atmospheric persistence of saturated aliphatics, unsaturated aliphatics, and aromatic toxic organics. The corresponding atmospheric half-lives for removal by chemical reactions range from a few hours for the most reactive toxics (chloroprene, hexachlorocyclo-pentadiene, cresols, nitrosamines, maleic anhydride) to several months for the least reactive compounds (nitrobenzene, methyl bromide, phosgene).

  4. Chemical reactions between Venus' surface and atmosphere - An update. (Invited)

    NASA Astrophysics Data System (ADS)

    Treiman, A. H.

    2013-12-01

    The surface of Venus, at ~740K, is hot enough to allow relatively rapid chemical reactions between it and the atmosphere, i.e. weathering. Venus chemical weathering has been explored in detail [1], to the limits of available data. New data from Venus Express (VEx) and new ideas from exoplanets have sparked a modest renewal of interest in Venus weathering. Venus' surface cannot be observed in visible light, but there are several NIR ';windows' through its atmosphere that allow surface imaging. The VIRTIS spectrometer on VEx viewed the surface through one window [2]; emissivity variations among lava flows on Imdr and Themis Regios have been explained as varying degrees of weathering, and thus age [3]. The VMC camera on VEx also provides images through a NIR window, which suggest variable degrees of weathering on some basaltic plains [4]. Indirect evidence for weathering may come from varying SO2 abundance at Venus' cloud tops; repeated rapid increases and gradual declines may represent volcanic eruptions followed by weathering to form sulfate minerals [5]. Continued geochemical modeling relevant to Venus weathering is motivated by expolanet studies [6]. Models have been extended to hypothetical exo-Venuses of different temperatures and surface compositions [7]. The idea that Venus' atmosphere composition can be buffered by reaction with its surface was explored in detail, and the derived constraint extended to other types of planets [8]. Several laboratories are investigating Venus weathering, motivated in part by the hope that they can provide real constraints on timescales of Venus volcanism [3]. Aveline et al. [9] are extending early studies [10] by reacting rocks and minerals with concentrated SO2 (to accelerate reaction rates to allow detectability of products). Kohler et al. [11] are investigating the stability of metals and chalcogenides as possible causes of the low-emissivity surfaces at high elevations. Berger and Aigouy [12] studied rock alteration on a

  5. Kinetics, mechanisms and products of reactions of Criegee intermediates

    NASA Astrophysics Data System (ADS)

    Orr-Ewing, Andrew

    The atmospheric ozonolysis of alkenes such as isoprene produces Criegee intermediates which are increasingly recognized as important contributors to oxidation chemistry in the Earth's troposphere. Stabilized Criegee intermediates are conveniently produced in the laboratory by ultraviolet photolysis of diiodoalkanes in the presence of O2, and can be detected by absorption spectroscopy using their strong electronic bands in the near ultraviolet region. We have used these techniques to study a wide range of reactions of Criegee intermediates, including their self-reactions, and reactions with carboxylic acids and various other trace atmospheric constituents. In collaboration with the Sandia National Laboratory group led by Drs C.A. Taatjes and D.L. Osborn, we have used photoionization and mass spectrometry methods, combined with electronic structure calculations, to characterize the products of several of these reactions. Our laboratory studies determine rate coefficients for the Criegee intermediate reactions, many of which prove to be fast. In the case of reactions with carboxylic acids, a correlation between the dipole moments of the reactants and the reaction rate coefficients suggests a dipole-capture controlled reaction and allows us to propose a structure-activity relationship to predict the rates of related processes. The contributions of these various Criegee intermediate reactions to the chemistry of the troposphere have been assessed using the STOCHEM-CRI global atmospheric chemistry model. This work was supported by NERC grant NE/K004905/1.

  6. Theoretical studies of atmospheric reaction mechanisms in the troposphere.

    PubMed

    Vereecken, Luc; Francisco, Joseph S

    2012-10-07

    The chemistry of the atmosphere encompasses a vast number of reactions acting on a plethora of intermediates. These reactions, occurring sequentially and in parallel, give rise to intertwined and irreducible mechanisms describing the complex chemical transformations of organic and inorganic compounds in the atmosphere. The complexity of this system is that it requires combined experimental, theoretical, and modeling approaches to elucidate the characteristics of the individual reactions, and their mutual interaction. In this review, we describe recent results from quantum chemical and theoretical kinetic studies of relevance to atmospheric chemistry. The review first summarizes the most commonly used theoretical methodologies. It then examines the VOC oxidation initiation channels by OH, O(3), NO(3) and Cl, followed by the reactions of the alkyl, alkoxy, alkylperoxy and Criegee intermediates active in the subsequent oxidation steps. Specific systems such as the oxidation of aromatics and the current state of knowledge on OH-regeneration in VOC oxidation are also discussed, as well as some inorganic reactions.

  7. Atmospheric products from the Upper Atmosphere Research Satellite (UARS)

    NASA Technical Reports Server (NTRS)

    Ahmad, Suraiya P.; Johnson, James E.; Jackman, Charles H.

    2003-01-01

    This paper provides information on the products available at the NASA Goddard Earth Sciences (GES) Distributed Active Archive Center (DAAC) from the Upper Atmosphere Research Satellite (UARS) mission. The GES DAAC provides measurements from the primary UARS mission, which extended from launch in September 1991 through September 2001. The ten instruments aboard UARS provide measurements of atmospheric trace gas species, dynamical variables, solar irradiance input, and particle energy flux. All standard Level 3 UARS products from all ten instruments are offered free to the public and science user community. The Level 3 data are geophysical parameters, which have been transformed into a common format and equally spaced along the measurement trajectory. The UARS data have been reprocessed several times over the years following improvements to the processing algorithms. The UARS data offered from the GES DAAC are the latest versions of each instrument. The UARS data may be accessed through the GES DAAC website at

  8. Theoretical study on the mechanism and kinetics of acetaldehyde and hydroperoxyl radical: An important atmospheric reaction

    NASA Astrophysics Data System (ADS)

    Farnia, Solaleh; Vahedpour, Morteza; Abedi, Mostafa; Farrokhpour, Hossein

    2013-09-01

    A systematic theoretical study was performed on the mechanism and kinetics of the atmospheric reaction of acetaldehyde (CH3CHO) and hydroperoxyl radical (HO2) in the gas phase. The DFT-B3LYP/6-311++G(3df,3pd) and CCSD(T)/6-311++G(d,p) methods were employed for calculations. Based on the calculations, this reaction leads to four different products through radical addition and hydrogen abstraction mechanisms which are very important in atmospheric and combustion chemistry. The favorable reaction paths begin with α-hydroxyethylperoxy radical, CH3CH(OO)OH, in a exothermic process and finally leads to the product P1 (CH3COOH + OH). The overall rate constants for favorite reaction paths have been calculated at different temperatures (200-2500 K).

  9. Products of reaction of OH radicals with α-pinene

    NASA Astrophysics Data System (ADS)

    Aschmann, Sara M.; Atkinson, Roger; Arey, Janet

    2002-07-01

    Products of the gas-phase reaction of α-pinene with OH radicals in the presence of NO have been investigated using gas chromatography with flame ionization detection to quantify pinonaldehyde and in situ atmospheric pressure ionization mass spectrometry in the negative ion mode to quantify selected other products as their NO2- adducts by utilizing C6-dihydroxycarbonyls and C6-hydroxynitrates formed in situ from the reaction of OH radicals with 1-hexene as an internal standard. The products quantified, and their molar formation yields, were: pinonaldehyde, 28 +/- 5% molecular weight 184 product (dihydroxycarbonyl), 19% (with an estimated uncertainty of a factor of ~2) molecular weight 200 product, 11% (with an estimated uncertainty of a factor of ~2). Together with a very approximate yield from our API-MS analyses for the formation of organic nitrates (~1%) and literature data for acetone (plus coproducts), ~65-70% of the reaction products and pathways are accounted for.

  10. Theoretical investigation on the mechanism of NO3 radical-initiated atmospheric reactions of phenanthrene

    NASA Astrophysics Data System (ADS)

    Zhao, Nan; Shi, Xiangli; Xu, Fei; Zhang, Qingzhu; Wang, Wenxing

    2017-07-01

    Phenanthrene is a polycyclic aromatic hydrocarbon from fossil fuel combustion with toxic properties. The products arising from atmospheric reaction can be more mutagenic and carcinogenic compared to unmodified phenanthrene, and are therefore important to be studied. The products of the specific NO3-radical reactions with phenanthrene where therefore investigated in this study by means of Density Functional Theory (DFT). The results show that the main products are proposed to be 10-(nitrooxy)-10-hydro-phenanthrene-9-one, 2,2‧-diformylbiphenyl, 9,10-phenanthrenequinone, 9-fluorenone and dibenzopyranone. 10-(nitrooxy)-10-hydro-phenanthrene-9-one and 2,2‧-diformylbiphenyl are classified as first-generation products which are subject to secondary reactions to produce 9,10-phenanthrenequinone, 9-fluorenone and dibenzopyranone. The rate constants of elementary reactions were assessed by Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The atmospheric lifetime of Phe determined by the gas-phase reaction with NO3 is estimated to be 1.8 h, based on the calculated overall rate constant of 3.04 × 10-13 cm3 molecule-1 s-1 at 298 K and 1 atm. Combined with available experimental observation, this work should help to clarify the transformation and potential health risk of Phe in the atmosphere.

  11. Atmospheric Production of Perchlorate on Earth and Mars

    NASA Astrophysics Data System (ADS)

    Claire, M.; Catling, D. C.; Zahnle, K. J.

    2009-12-01

    Natural production and preservation of perchlorate on Earth occurs only in arid environments. Isotopic evidence suggests a strong role for atmospheric oxidation of chlorine species via pathways including ozone or its photochemical derivatives. As the Martian atmosphere is both oxidizing and drier than the driest places on Earth, we propose an atmospheric origin for the Martian perchlorates measured by NASA's Phoenix Lander. A variety of hypothetical formation pathways can be proposed including atmospheric photochemical reactions, electrostatic discharge, and gas-solid reactions. Here, we investigate gas phase formation pathways using a 1-D photochemical model (Catling et al. 2009, accepted by JGR). Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we start with a study of the means to produce Atacama perchlorate. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. These results are sensitive to estimated reaction rates for ClO3 species. The feasibility of gas phase production for the Atacama provides justification for further investigations of gas phase photochemistry as a possible source for Martian perchlorate. In addition to the Atacama results, we will present a preliminary study incorporating chlorine chemistry into an existing Martian photochemical model (Zahnle et al. JGR 2008).

  12. Photochemical reactions of cyanoacetylene and dicyanoacetylene: Possible processes in Titan's atmosphere

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.; Guillemin, J. C.

    1991-01-01

    Titan has an atmosphere which is subject to dramatic chemical evolution due mainly to the dramatic effect of the UV flux from the Sun. The energetic solar photons and other particles are converting the methane-nitrogen atmosphere into the unsaturated carbon compounds observed by the Voyager probes. These same solar photons are also converting some of these unsaturated reaction products into the aerosols observed in the atmosphere which obscure the view of the surface of Titan. In particular, the photochemical reactions of cyanoacetylene, dicyanoacetylene, acetylene and ethylene may result in the formation of the higher hydrocarbons and polymers which result in the aerosols observed in Titan's atmosphere. Polymers are the principal reaction products formed by irradiation of cyanoacetylene and dicyanoacetylene. Irradiation of cyanoacetylene with 185 nm of light also yields 1,3,5-tricyanobenzene while irradiation at 254 nm yields 1,2,4-tricyanobenzene and tetracyano cyclooctatetraenes. Photolyses of mixtures of cyanoacetylene and acetylene yields mono- and di- cyanobenzenes. The 1-Cyanocyclobutene is formed from the photochemical addition of cyanoacetylene with ethylene. The photolysis of dicyanoacetylene with acetylene yields 2,3-dicyano-1,3-butadiene and 1,2-dicyanobenzene. Tetracyano cyclooctatetraene products were also observed in the photolysis of mixtures of dicyanoacetylene and acetylene with 254 nm light. The 1,2-Dicyano cyclobutene is obtained from the photolysis dicyanoacetylene and ethylene. Reaction mechanisms will be proposed to explain the observed photoproducts.

  13. Uptake and reaction of atmospheric organic vapours on organic films.

    PubMed

    Donaldson, D J; Mmereki, Baagi T; Chaudhuri, Sri R; Handley, Susannah; Oh, Megan

    2005-01-01

    Films composed in whole or in part of organic compounds represent an important atmospheric interface. Urban surfaces are now known to be coated with a film ("grime") whose chemical composition somewhat resembles that of urban atmospheric aerosols. Such films may act as media in which atmospheric trace gases may be sequestered (leading to their removal from the gas phase); they may also act as reactive media, either as a "solvent" or as a source of reagents. Organic coatings on aqueous surfaces are also important, not just on ocean and lake surfaces ("biofilms") but also on the surfaces of fogwaters and atmospheric aerosol particles. We have initiated experimental uptake studies of trace gases into simple proxies for urban organic films using two techniques: a Knudsen cell effusion reactor and a laser-induced fluorescence method. We will discuss our first results on non-reactive uptake of organic compounds by organic films we use as proxies for urban grime coatings. In general, the measured uptake coefficients appear to track the octanol-air partition coefficients, at least qualitiatively. We have also measured the kinetics of reactions between gas-phase ozone and small polycyclic aromatic hydrocarbons (PAHs), when these are adsorbed at the air-aqueous interface or incorporated into an organic film. Reactions at the "clean" air-water interface and at a coated interface consisting of a monolayer of various amphiphilic organic compounds all follow a Langmuir-Hinshelwood mechanism, in which ozone first adsorbs to the air-aqueous interface, then reacts with already adsorbed PAH. By contrast, the reaction in the pure organic film occurs in the bulk phase. Under some circumstances, heterogeneous oxidation of PAHs by ozone may be as important in the atmosphere as their gas phase oxidation by OH.

  14. Insights into secondary reactions occurring during atmospheric ablation of micrometeoroids

    NASA Astrophysics Data System (ADS)

    Court, Richard W.; Tan, Jonathan

    2016-06-01

    Ablation of micrometeoroids during atmospheric entry yields volatile gases such as water, carbon dioxide, and sulfur dioxide, capable of altering atmospheric chemistry and hence the climate and habitability of the planetary surface. While laboratory experiments have revealed the yields of these gases during laboratory simulations of ablation, the reactions responsible for the generation of these gases have remained unclear, with a typical assumption being that species simply undergo thermal decomposition without engaging in more complex chemistry. Here, pyrolysis-Fourier transform infrared spectroscopy reveals that mixtures of meteorite-relevant materials undergo secondary reactions during simulated ablation, with organic matter capable of taking part in carbothermic reduction of iron oxides and sulfates, resulting in yields of volatile gases that differ from those predicted by simple thermal decomposition. Sulfates are most susceptible to carbothermic reduction, producing greater yields of sulfur dioxide and carbon dioxide at lower temperatures than would be expected from simple thermal decomposition, even when mixed with meteoritically relevant abundances of low-reactivity Type IV kerogen. Iron oxides were less susceptible, with elevated yields of water, carbon dioxide, and carbon monoxide only occurring when mixed with high abundances of more reactive Type III kerogen. We use these insights to reinterpret previous ablation simulation experiments and to predict the reactions capable of occurring during ablation of carbonaceous micrometeoroids in atmospheres of different compositions.

  15. Liquid water production from atmospheric sources

    NASA Astrophysics Data System (ADS)

    Matthews, John D.; Clarke, Norman P.

    1991-02-01

    The purpose of this effort was to assess the feasibility of developing a desiccant system to produce potable water from atmospheric sources that is compatible with military constraints. Goals were: (1) to examine desiccant technology, investigate methods of using available desiccants to collect atmospheric moisture, (2) develop a conceptual model of a desiccant water production system, and (3) develop a mathematical model to simulate the operation of the conceptual model. Results show that a desiccant system can produce large quantities of potable water using relatively small amounts of fuel for heat and fan power. The focus of this project was using a liquid desiccant (such as triethylene glycol) in an absorption-distillation cycle. This report documents the theoretical analysis of a hypothetical liquid desiccant based system for producing liquid water through collection of atmospheric moisture. Estimates are made of cost, weight and water production rate for the hypothetical system.

  16. Atmospheric trident production for probing new physics

    NASA Astrophysics Data System (ADS)

    Ge, Shao-Feng; Lindner, Manfred; Rodejohann, Werner

    2017-09-01

    We propose to use atmospheric neutrinos as a powerful probe of new physics beyond the Standard Model via neutrino trident production. The final state with double muon tracks simultaneously produced from the same vertex is a distinctive signal at large Cherenkov detectors. We calculate the expected event numbers of trident production in the Standard Model. To illustrate the potential of this process to probe new physics we obtain the sensitivity on new vector/scalar bosons with coupling to muon and tau neutrinos.

  17. Reaction of SO2 with OH in the atmosphere.

    PubMed

    Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G

    2017-03-15

    The OH + SO2 reaction plays a critical role in understanding the oxidation of SO2 in the atmosphere, and its rate constant is critical for clarifying the fate of SO2 in the atmosphere. The rate constant of the OH + SO2 reaction is calculated here by using beyond-CCSDT correlation energy calculations for a benchmark, validated density functional methods for direct dynamics, canonical variational transition state theory with anharmonicity and multidimensional tunneling for the high-pressure rate constant, and system-specific quantum RRK theory for pressure effects; the combination of these methods can compete in accuracy with experiments. There has been a long-term debate in the literature about whether the OH + SO2 reaction is barrierless, but our calculations indicate a positive barrier with an transition structure that has an enthalpy of activation of 0.27 kcal mol(-1) at 0 K. Our results show that the high-pressure limiting rate constant of the OH + SO2 reaction has a positive temperature dependence, but the rate constant at low pressures has a negative temperature dependence. The computed high-pressure limiting rate constant at 298 K is 1.25 × 10(-12) cm(3) molecule(-1) s(-1), which agrees excellently with the value (1.3 × 10(-12) cm(3) molecule(-1) s(-1)) recommended in the most recent comprehensive evaluation for atmospheric chemistry. We show that the atmospheric lifetime of SO2 with respect to oxidation by OH depends strongly on altitude (in the range 0-50 km) due to the falloff effect. We introduce a new interpolation procedure for fitting the combined temperature and pressure dependence of the rate constant, and it fits the calculated rate constants over the whole range with a mean unsigned error of only 7%. The present results provide reliable kinetics data for this specific reaction, and also they demonstrate convenient theoretical methods that can be reliable for predicting rate constants of other gas-phase reactions.

  18. Atmospheric Reactions of a Series of Hexenols with OH Radical and Ozone

    NASA Astrophysics Data System (ADS)

    Gai, Yanbo; Lin, Xiaoxiao; Ma, Qiao; Yang, Chengqiang; Zhao, Weixiong; Zhang, Weijun

    2016-04-01

    C6 hexenols are one of the most significant groups of biogenic volatile organic compounds (BVOCs). Because of their antibacterial properties, C6 hexenols can be emitted by a wide number of plants in response to changes in the ambient environment. The oxidation of these compounds in the atmosphere is involved in the formation of tropospheric ozone and secondary organic aerosols (SOA), thus causing significant effects on atmospheric chemistry and the climate. The lack of corresponding kinetic parameters and product information of their oxidation reactions will result in incomplete atmospheric chemical mechanisms and models. In this paper, we will overview our recent research progress on the study of the atmospheric reactions of a series of C6 hexenols with OH radicals and ozone. A series of studies were conducted using both experimental and theoretical methods. Corresponding rate constants were obtained, and reaction mechanisms were also analyzed. It could be concluded that both the nature of the substituent and its position play a fundamental role in the reactivity of the C6 hexenols toward OH radicals and O3. An activating effect of the -OH group in OH radical reactions was found, thus making the H-abstraction channel non-negligible in reactions of these unsaturated alcohols with OH radicals. The removal of these C6 hexenols by ozone also showed great importance and could be competitive with the major recognized sinks by OH radicals. These studies are of great significance for understanding the mechanism of atmospheric chemical reactions of hexenols and improving the atmospheric chemistry model. Experimental detail and corresponding results will be presented. Acknowledgements. This work was supported by the National Natural Science Foundation of China (21307137, 41575125 and 91544228), and the Natural Science Foundation of Anhui Province (1508085J03).

  19. The OH-initiated atmospheric reaction mechanism and kinetics for levoglucosan emitted in biomass burning.

    PubMed

    Bai, Jing; Sun, Xiaomin; Zhang, Chenxi; Xu, Yisheng; Qi, Chuansong

    2013-11-01

    Levoglucosan is a typical molecular tracer of biomass-burning aerosols in the atmosphere. The mechanism for OH-initiated reaction with levoglucosan is studied at the level of MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p). The possible subsequent reactions in the presence of O2, NO and H2O are also taken into consideration. The study shows that the H atom abstraction from the C4-position by the OH radical is an energetically favorable pathway, and that the OH-initiated products contribute to the formation of SOA and atmospheric acidity. The kinetic calculation is performed and the rate constants are calculated over the temperature range of 200-1500 K, using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The rate constant of levoglucosan reacting with the OH radical at 298 K is 2.21×10(-13) cm(3) molecule(-1) s(-1) and the atmospheric lifetime is 26 days ([OH]=2.0×10(6) molecule cm(-3)). The equilibrium constants both in gas phase and aqueous are computed. The free energy ΔG indicates that, the subsequent reactions tend to take place more spontaneously once the reaction occurs. This work provides a comprehensive investigation about OH-initiated atmospheric reactions with levoglucosan, which is helpful for experiment and risk assessment.

  20. The OMI Atmospheric Science Data Products

    NASA Astrophysics Data System (ADS)

    Johnson, J. E.; Ahmad, S. P.; Levelt, P. F.; Bhartia, P. K.; Hilsenrath, E.; Leppelmeier, G. W.

    2003-12-01

    The Ozone Monitoring Instrument (OMI), will provide measurements in the UV and Visible spectral regions (1560 wavelength bands between 270 and 500 nm with approximately 0.5 nm spectral resolution). OMI will continue the long-term Total Ozone Mapping Spectrometer (TOMS) column ozone record and will focus on monitoring the ozone layer, ozone depleting trace gases (BrO and OClO), atmospheric pollutants (tropospheric ozone, NO2, SO2, and HCHO), clouds and aerosols characteristics, and surface spectral UV irradiance and erythemal surface UV-B flux. OMI is a contribution of the Netherlands Agency for Aerospace Programs (NIVR) in collaboration with the Finnish Meteorological Institute (FMI), to NASA's Aura mission. It will be flown on the Aura spacecraft (early 2004) in a sun-synchronous polar orbit with equator crossing time approximately at 1:38 p.m in the ascending mode. The standard atmospheric chemistry and dynamics products derived from OMI, and from the other two Aura sensors, the High Resolution Dynamics Limb Sounder (HIRDLS) and the Microwave Limb Sounder (MLS), will be archived at the NASA GES DAAC. OMI atmospheric data products will provide continuity to the over 30 year long-term ozone data records obtained from the heritage atmospheric data missions including Nimbus-4 BUV and Nimbus-7 SBUV, and a series of TOMS instruments, also archived at the NASA GES DAAC. The standard satellite data sets, as well as regional subsets, related ancillary data sets, and data analysis tools are freely available to the public for the Earth System Science studies, environmental applications, and educational use. This presentation will provide an overview of the OMI instrument, data processing, data products, and the data services provided by the NASA GES DAAC's Upper Atmosphere Data Support team to the user in the areas of accessing data products, documentation, browse, and data analysis software.

  1. Upper atmosphere research: Reaction rate and optical measurements

    NASA Technical Reports Server (NTRS)

    Stief, L. J.; Allen, J. E., Jr.; Nava, D. F.; Payne, W. A., Jr.

    1990-01-01

    The objective is to provide photochemical, kinetic, and spectroscopic information necessary for photochemical models of the Earth's upper atmosphere and to examine reactions or reactants not presently in the models to either confirm the correctness of their exclusion or provide evidence to justify future inclusion in the models. New initiatives are being taken in technique development (many of them laser based) and in the application of established techniques to address gaps in the photochemical/kinetic data base, as well as to provide increasingly reliable information.

  2. Atmospheric Chemistry of Criegee Intermediates: Unimolecular Reactions and Reactions with Water.

    PubMed

    Long, Bo; Bao, Junwei Lucas; Truhlar, Donald G

    2016-11-02

    Criegee intermediates are produced in the ozonolysis of unsaturated hydrocarbons in the troposphere, and understanding their fate is a prerequisite to modeling climate-controlling atmospheric aerosol formation. Although some experimental and theoretical rate data are available, they are incomplete and partially inconsistent, and they do not cover the tropospheric temperature range. Here, we report quantum chemical rate constants for the reactions of stabilized formaldehyde oxide (CH2OO) and acetaldehyde oxide (syn-CH3CHOO and anti-CH3CHOO) with H2O and for their unimolecular reactions. Our results are obtained by combining post-CCSD(T) electronic structure benchmarks, validated density functional theory potential energy surfaces, and multipath variational transition state theory with multidimensional tunneling, coupled-torsions anharmonicity, and high-frequency anharmonicity. We consider two different types of reaction mechanisms for the bimolecular reactions, namely, (i) addition-coupled hydrogen transfer and (ii) double hydrogen atom transfer (DHAT). First, we show that the MN15-L exchange-correlation functional has kJ/mol accuracy for the CH2OO + H2O and syn-CH3CHOO + H2O reactions. Then we show that, due to tunneling, the DHAT mechanism is especially important in the syn-CH3CHOO + H2O reaction. We show that the dominant pathways for reactions of Criegee intermediates depend on altitude. The results we obtain eliminate the discrepancy between experiment and theory under those conditions where experimental results are available, and we make predictions for the full range of temperatures and pressures encountered in the troposphere and stratosphere. The present results are an important cog in clarifying the atmospheric fate and oxidation processes of Criegee intermediates, and they also show how theoretical methods can provide reliable rate data for complex atmospheric processes.

  3. Energy distribution among reaction products. IV.

    NASA Technical Reports Server (NTRS)

    Maylotte, D. H.; Polanyi, J. C.; Woodall, K. B.

    1972-01-01

    Use of an infrared chemiluminescence technique, called 'Method II,' or the 'method of arrested relaxation' to measure the distribution of energy among products of the Cl + HI and Cl + DI reactions. Preliminary results are also given for the Br + HI and Cl + HBr reactions. Instead of measuring vibrational relaxation, Method II attempts to arrest vibrational and rotational relaxation by the rapid removal of excited products at a cold surface.

  4. Reaction products of ozone: a review.

    PubMed Central

    Glaze, W H

    1986-01-01

    The reaction products of ozone that form during the oxidation of compounds found in aqueous media are reviewed. Reaction products of ozone are well documented only for a limited number of substrates, and mechanistic information is quite rare. Decomposition of ozone during its reactions, sometimes induced by matrix impurities or by the by-products of the reactions, will generate highly reactive hydroxyl radicals. Thus, even reactions occurring at pH less than 7 may have radical character. More complete destruction of organic substrates may be enhanced by using catalysts, such as ultraviolet radiation or hydrogen peroxide, to accelerate radical formation. However, complete mineralization is generally not practical economically, so partially oxidized by-products can be expected under typical treatment conditions. Ozone by-products tend to be oxygenated compounds that are usually, but not always, more biodegradable and less toxic than xenobiotic precursors. Of particular interest are hydroperoxide by-products, which may have escaped detection because of their lability, and unsaturated aldehydes. Inorganic by-products tend to be in high oxidation states, which in some cases (e.g., some metallic elements) may lead to enhanced removal by flocculation and sedimentation. In other cases oxidation may lead to formation of reactive species such as hypobromous acid from bromide ion or permanganate from manganous ion. In general, more research is required before a valid assessment of the risks of ozone by-products can be made. PMID:3545802

  5. Nylon production: An unknown source of atmospheric nitrous oxide

    SciTech Connect

    Thiemens, M.H.; Trogler, W.C. )

    1991-02-22

    Nitrous oxide in the earth's atmosphere contributes to catalytic stratospheric ozone destruction and is also a greenhouse gas component. A precise budgetary accounting of N{sub 2}O sources has remained elusive, and there is an apparent lack of source identification. One source of N{sub 2}O is as a by-product in the manufacture of nylon, specifically in the preparation of adipic acid. Characterization of the reaction N{sub 2}O stoichiometry and its isotopic composition with a simulated industrial adipic acid synthesis indicates that because of high rates of global adipic acid production, this N{sub 2}O may account for {approximately}10% of the increase observed for atmospheric N{sub 2}O.

  6. Atmospheric production of glycolaldehyde under hazy prebiotic conditions.

    PubMed

    Harman, Chester E; Kasting, James F; Wolf, Eric T

    2013-04-01

    The early Earth's atmosphere, with extremely low levels of molecular oxygen and an appreciable abiotic flux of methane, could have been a source of organic compounds necessary for prebiotic chemistry. Here, we investigate the formation of a key RNA precursor, glycolaldehyde (2-hydroxyacetaldehyde, or GA) using a 1-dimensional photochemical model. Maximum atmospheric production of GA occurs when the CH4:CO2 ratio is close to 0.02. The total atmospheric production rate of GA remains small, only 1 × 10(7) mol yr(-1). Somewhat greater amounts of GA production, up to 2 × 10(8) mol yr(-1), could have been provided by the formose reaction or by direct delivery from space. Even with these additional production mechanisms, open ocean GA concentrations would have remained at or below ~1 μM, much smaller than the 1-2 M concentrations required for prebiotic synthesis routes like those proposed by Powner et al. (Nature 459:239-242, 2009). Additional production or concentration mechanisms for GA, or alternative formation mechanisms for RNA, are needed, if this was indeed how life originated on the early Earth.

  7. Hyperon production from neutrino-nucleon reaction

    SciTech Connect

    Wu, Jia -Jun; Zou, Bing -Song

    2015-04-10

    The neutrino induced hyperon production processes ν¯e/μ + p → e++ + π + Λ/Σ may provide a unique clean place for studying low energy πΛ/Σ interaction and hyperon resonances below KN threshold. The production rates for some neutrino induced hyperon production processes are estimated with theoretical models. Lastly, suggestions are made for the study of hyperon production from neutrino–nucleon reaction at present and future neutrino facilities.

  8. Hyperon production from neutrino-nucleon reaction

    DOE PAGES

    Wu, Jia -Jun; Zou, Bing -Song

    2015-04-10

    The neutrino induced hyperon production processes ν¯e/μ + p → e+/μ+ + π + Λ/Σ may provide a unique clean place for studying low energy πΛ/Σ interaction and hyperon resonances below KN threshold. The production rates for some neutrino induced hyperon production processes are estimated with theoretical models. Lastly, suggestions are made for the study of hyperon production from neutrino–nucleon reaction at present and future neutrino facilities.

  9. Kinetic and mechanistic study of the atmospheric reaction of MBO331 with Cl atoms

    NASA Astrophysics Data System (ADS)

    Rodríguez, Diana; Rodríguez, Ana; Garzón, Andrés; Granadino-Roldán, José M.; Soto, Amparo; Aranda, Alfonso; Notario, Alberto

    2012-12-01

    The present work deals with the reaction of 3-methyl-3-buten-1-ol (MBO331) with Cl atoms, which has been investigated by gas chromatography with flame ionization detection (GC-FID) at atmospheric pressure in N2 or air, using the relative rate technique. The rate constant reaction at 298 ± 1 K was found to be (5.01 ± 0.70) × 10-10 cm3 molecule-1 s-1, using cyclohexane, octane and 1-butene as a reference compounds. The temperature dependence for the reaction was studied within the 298-333 K range. Additionally, a product identification under atmospheric conditions has been performed for the first time by GC-MS, with 3-methyl-3-butenal, methacrolein and chloroacetone being observed as degradation products. A theoretical study on the reaction at the QCISD(T)/6-311G**//MP2/6-311G** level was also carried out to obtain more information on the mechanism. From the theoretical study it can be predicted that Cl addition to the double bond proceeds through lower energy barriers than H-abstraction pathways and therefore is energetically favoured. Finally, atmospheric implications of the results obtained are discussed.

  10. Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

    NASA Technical Reports Server (NTRS)

    David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

    1997-01-01

    Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

  11. Reaction of cobalt in SO2 atmospheric at elevated temperatures

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1983-01-01

    The reaction rate of cobalt in SO2 argon environments was measured at 650 C, 700 C, 750 C and 800 C. Product scales consist primarily of an interconnected sulfide phase in an oxide matrix. At 700 C to 800 C a thin sulfide layer adjacent to the metal is also observed. At all temperatures, the rapid diffusion of cobalt outward through the interconnected sulfide appears to be important. At 650 C, the reaction rate slows dramatically after five minutes due to a change in the distribution of these sulfides. At 700 C and 750 C the reaction is primarily diffusion controlled values of diffusivity of cobalt (CoS) calculated from this work show favorable agreement with values of diffusivity of cobalt (CoS) calculated from previous sulfidation work. At 800 C, a surface step becomes rate limiting.

  12. Reaction of cobalt in SO2 atmospheres at elevated temperatures

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1984-01-01

    The reaction rate of cobalt in SO2 argon environments was measured at 650 C, 700 C, 750 C and 800 C. Product scales consist primarily of an interconnected sulfide phase in an oxide matrix. At 700 C to 800 C, a thin sulfide layer adjacent to the metal is also observed. At all temperatures, the rapid diffusion of cobalt outward through the interconnected sulfide appears to be important. At 650 C, the reaction rate slows dramatically after five minutes due to a change in the distribution of these sulfides. At 700 C and 750 C, the reaction is primarily diffusion controlled; values of diffusivity of cobalt (CoS) calculated from this work show favorable agreement with values of diffusivity of cobalt (CoS) calculated from previous sulfidation work. At 800 C, a surface step becomes rate limiting. Previously announced in STAR as N83-35104

  13. Reaction of cobalt in SO2 atmospheres at elevated temperatures

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1984-01-01

    The reaction rate of cobalt in SO2 argon environments was measured at 650 C, 700 C, 750 C and 800 C. Product scales consist primarily of an interconnected sulfide phase in an oxide matrix. At 700 C to 800 C, a thin sulfide layer adjacent to the metal is also observed. At all temperatures, the rapid diffusion of cobalt outward through the interconnected sulfide appears to be important. At 650 C, the reaction rate slows dramatically after five minutes due to a change in the distribution of these sulfides. At 700 C and 750 C, the reaction is primarily diffusion controlled; values of diffusivity of cobalt (CoS) calculated from this work show favorable agreement with values of diffusivity of cobalt (CoS) calculated from previous sulfidation work. At 800 C, a surface step becomes rate limiting. Previously announced in STAR as N83-35104

  14. Acid-catalyzed reactions of hexanal on sulfuric acid particles: Identification of reaction products

    NASA Astrophysics Data System (ADS)

    Garland, Rebecca M.; Elrod, Matthew J.; Kincaid, Kristi; Beaver, Melinda R.; Jimenez, Jose L.; Tolbert, Margaret A.

    While it is well established that organics compose a large fraction of the atmospheric aerosol mass, the mechanisms through which organics are incorporated into atmospheric aerosols are not well understood. Acid-catalyzed reactions of compounds with carbonyl groups have recently been suggested as important pathways for transfer of volatile organics into acidic aerosols. In the present study, we use the aerodyne aerosol mass spectrometer (AMS) to probe the uptake of gas-phase hexanal into ammonium sulfate and sulfuric acid aerosols. While both deliquesced and dry non-acidic ammonium sulfate aerosols showed no organic uptake, the acidic aerosols took up substantial amounts of organic material when exposed to hexanal vapor. Further, we used 1H-NMR, Fourier transform infrared (FTIR) spectroscopy and GC-MS to identify the products of the acid-catalyzed reaction of hexanal in acidic aerosols. Both aldol condensation and hemiacetal products were identified, with the dominant reaction products dependent upon the initial acid concentration of the aerosol. The aldol condensation product was formed only at initial concentrations of 75-96 wt% sulfuric acid in water. The hemiacetal was produced at all sulfuric acid concentrations studied, 30-96 wt% sulfuric acid in water. Aerosols up to 88.4 wt% organic/11.1 wt% H 2SO 4/0.5 wt% water were produced via these two dimerization reaction pathways. The UV-VIS spectrum of the isolated aldol condensation product, 2-butyl 2-octenal, extends into the visible region, suggesting these reactions may impact aerosol optical properties as well as aerosol composition. In contrast to previous suggestions, no polymerization of hexanal or its products was observed at any sulfuric acid concentration studied, from 30 to 96 wt% in water.

  15. Chemical Characterization of Secondary Organic Aerosol Formed from Atmospheric Aqueous-phase Reactions of Phenolic Compounds

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Anastasio, C.; Zhang, Q.

    2012-12-01

    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phenol, guaiacol and syringol) with two oxidants - excited triplet states (3C*) of non-phenolic aromatic carbonyls and hydroxyl radical (OH). By employing four analytical methods including high-resolution aerosol mass spectrometry, total organic carbon analysis, ion chromatography, and liquid chromatography-mass spectrometry, we thoroughly characterize the chemical compositions of the low volatility reaction products of phenols and propose formation mechanisms based on this information. Our results indicate that phenolic SOA is highly oxygenated, with O/C ratios in the range of 0.83-1.03, and that the SOA of phenol is usually more oxidized than those of guaiacol and syringol. Among the three precursors, syringol generates the largest fraction of higher molecular weight (MW) products. For the same precursor, the SOA formed via reaction with 3C* is less oxidized than that formed via reaction with OH. In addition, oxidation by 3C* enhances the formation of higher MW species, including phenolic dimers, higher oligomers and hydroxylated products, compared to reactions initiated by OH, which appear to favor the formation of organic acids. However, our results indicate that the yields of small organic acids (e.g., formate, acetate, oxalate, and malate) are low for both reaction pathways, together accounting for less than 5% of total SOA mass.

  16. Atmospheric Processing Module for Mars Propellant Production

    NASA Technical Reports Server (NTRS)

    Muscatello, Anthony; Gibson, Tracy; Captain, James; Athman, Robert; Nugent, Matthew; Parks, Steven; Devor, Robert

    2013-01-01

    The multi-NASA center Mars Atmosphere and Regolith COllector/PrOcessor for Lander Operations (MARCO POLO) project was established to build and demonstrate a methane/oxygen propellant production system in a Mars analog environment. Work at the Kennedy Space Center (KSC) Applied Chemistry Laboratory is focused on the Atmospheric Processing Module (APM). The purpose of the APM is to freeze carbon dioxide from a simulated Martian atmosphere containing the minor components nitrogen, argon, carbon monoxide, and water vapor at Martian pressures (8 torr) by using dual cryocoolers with alternating cycles of freezing and sublimation. The resulting pressurized CO2 is fed to a methanation subsystem where it is catalytically combined with hydrogen in a Sabatier reactor supplied by the Johnson Space Center (JSC) to make methane and water vapor. We first used a simplified once-through setup and later employed a HiCO2 recycling system to improve process efficiency. This presentation and paper will cover (1) the design and selection of major hardware items, such as the cryocoolers, pumps, tanks, chillers, and membrane separators, (2) the determination of the optimal cold head design and flow rates needed to meet the collection requirement of 88 g CO2/hr for 14 hr, (3) the testing of the CO2 freezer subsystem, and (4) the integration and testing of the two subsystems to verify the desired production rate of 31.7 g CH4/hr and 71.3 g H20/hr along with verification of their purity. The resulting 2.22 kg of CH4/O2 propellant per 14 hr day (including O2 from electrolysis of water recovered from regolith, which also supplies the H2 for methanation) is of the scale needed for a Mars Sample Return mission. In addition, the significance of the project to NASA's new Mars exploration plans will be discussed.

  17. Atmospheric Processing Module for Mars Propellant Production

    NASA Technical Reports Server (NTRS)

    Muscatello, Anthony; Gibson, Tracy; Captain, James; Athman, Robert; Nugent, Matthew; Parks, Steven; Devor, Robert

    2013-01-01

    The multi-NASA center Mars Atmosphere and Regolith COllector/PrOcessor for Lander Operations (MARCO POLO) project was established to build and demonstrate a methane/oxygen propellant production system in a Mars analog environment. Work at the Kennedy Space Center (KSC) Applied Chemistry Laboratory is focused on the Atmospheric Processing Module (APM). The purpose of the APM is to freeze carbon dioxide from a simulated Martian atmosphere containing the minor components nitrogen, argon, carbon monoxide, and water vapor at Martian pressures (approx.8 torr) by using dual cryocoolers with alternating cycles of freezing and sublimation. The resulting pressurized CO2 is fed to a methanation subsystem where it is catalytically combined with hydrogen in a Sabatier reactor supplied by the Johnson Space Center (JSC) to make methane and water vapor. We first used a simplified once-through setup and later employed a HiCO2 recycling system to improve process efficiency. This presentation and paper will cover (1) the design and selection of major hardware items, such as the cryocoolers, pumps, tanks, chillers, and membrane separators, (2) the determination of the optimal cold head design and flow rates needed to meet the collection requirement of 88 g CO2/hr for 14 hr, (3) the testing of the CO2 freezer subsystem, and (4) the integration and testing of the two subsystems to verify the desired production rate of 31.7 g CH4/hr and 71.3 g H2O/hr along with verification of their purity. The resulting 2.22 kg of CH4/O2 propellant per 14 hr day (including O2 from electrolysis of water recovered from regolith, which also supplies the H2 for methanation) is of the scale needed for a Mars Sample Return mission. In addition, the significance of the project to NASA's new Mars exploration plans will be discussed.

  18. Laboratory studies on N(2D) reactions of relevance to the chemistry of planetary atmospheres

    NASA Astrophysics Data System (ADS)

    Balucani, N.; Casavecchia, P.

    Molecular nitrogen is a very stable molecule, practically inert from a chemical point of view. For a nitrogen chemistry to occur in the planetary atmospheres which contain N2 , it is necessary to transform it into an active form, such as atoms or ions. As far as the production of atomic nitrogen in the upper atmospheres of planets (like Mars) or moons (like Titan) is concerned, several processes - as N2 dissociation induced by electron impact, EUV photolysis (λ <80 nm) and dissociative photoionization, or galactic cosmic ray absorption and N+ dissociative recombination all 2 lead to atomic nitrogen, notably in the ground, 4 S3/2 , and first electronically excited, 2 D3/2,5/2 , states with comparable yields. The radiative lifetimes of the metastable states 2 D3/2 and 2 D5/2 are quite long (12.3 and 48 hours, respectively), because the transition from a doublet to a quartet state is strongly forbidden. In addition, the physical quenching of N(2 D) is often a slow process and in some important cases the main fate of N(2 D) is chemical reaction with other constituents of the planetary atmospheres. The production of N atoms in the 2 D state is an important fact, because N(4 S) atoms exhibit very low reactivity with closed-shell molecules and the probability of collision with an open-shell radical is small. Unfortunately laboratory experiments on the gas-phase reactions of N(2 D) have been lacking until recently, because of serious experimental difficulties in studying these reactive systems. Accurate kinetic data on the reactions of N(2 D) with the some molecules of relevance to the chemistry of planetary atmospheres have finally become available in the late 90's, but a better knowledge of the reactive behavior requires a dynamical investigation of N(2 D) reactions. The capability of generating intense continuous beams of N(2 D) achieved in our laboratory some years ago has opened up the possibility of studying the reactive scattering of this species under single

  19. Trotter products and reaction-diffusion equations

    NASA Astrophysics Data System (ADS)

    Popescu, Emil

    2010-01-01

    In this paper, we study a class of generalized diffusion-reaction equations of the form , where A is a pseudodifferential operator which generates a Feller semigroup. Using the Trotter product formula we give a corresponding discrete time integro-difference equation for numerical solutions.

  20. Neutrinos from charm production in the atmosphere

    SciTech Connect

    Enberg, Rikard

    2014-11-18

    Atmospheric neutrinos are produced in interactions of cosmic rays with Earth's atmosphere. At very high energy, the contribution from semi-leptonic decays of charmed hadrons, known as the prompt neutrino flux, dominates over the conventional flux from pion and kaon decays. This is due to the very short lifetime of the charmed hadrons, which therefore do not lose energy before they decay. The calculation of this process is difficult because the Bjorken-x at which the parton distribution functions are evaluated is very small. This is a region where QCD is not well understood, and large logarithms must be resummed. Available parton distribution functions are not known at such small x and extrapolations must be made. Theoretically, the fast rise of the structure functions for small x ultimately leads to parton saturation. This contribution describes the 'ERS' [1] calculation of the prompt neutrino flux, which includes parton saturation effects in the QCD production cross section of charm quarks. The ERS flux calculation is used by e.g. the IceCube collaboration as a standard benchmark background. We are now updating this calculation to take into account the recent LHC data on the charm cross section, as well as recent theoretical developments in QCD. Some of the issues involved in this calculation are described.

  1. The reactions of cobalt, iron and nickel in SO-2 atmospheres: Similarities and differences

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1984-01-01

    The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibits similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

  2. The reactions of cobalt, iron and nickel in SO2 atmospheres Similarities and differences

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1985-01-01

    The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibit similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

  3. The reactions of cobalt, iron and nickel in SO2 atmospheres Similarities and differences

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.; Worrell, W. L.

    1985-01-01

    The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibit similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

  4. Photochemical reaction between triclosan and nitrous acid in the atmospheric aqueous environment

    NASA Astrophysics Data System (ADS)

    Ma, Jianzhong; Zhu, Chengzhu; Lu, Jun; Lei, Yu; Wang, Jizhong; Chen, Tianhu

    2017-05-01

    Nitrous acid (HONO) is an important tropospheric pollutant and a major source of hydroxyl radical in the atmospheric gas phase. However, studies on the role of HONO in atmospheric aqueous phase chemistry processes are relatively few. The present work investigated the photochemical reaction of HONO with triclosan (TCS), which is an emerging contaminant, using a combination of laser flash photolysis spectrometry and gas chromatography mass spectrometry. With these techniques, the reaction pathway of HONO with TCS was proposed by directly monitoring the transient species and detecting the stable products. ·OH was generated from the photodissociation of the HONO aqueous solution and attacked TCS molecules on different sites to produce the TCS-OH adducts with a second-order rate constant of 1.11 × 109 L mol-1 s-1. The ·OH added a C atom adjacent to the ether bond in the aromatic ring of TCS and self-decayed when the ether bond broke. The intermediates generated from the addition of ·OH to the benzene ring of the TCS molecular structure were immediately nitrated by HONO, which played a key role in the formation process of nitrocompounds. An atmospheric model suggests that the aqueous oxidation of TCS by ·OH is a major reaction at high liquid water concentrations, and the photolysis of TCS dominates under low-humidity conditions.

  5. Atmospheric Processing Module for Mars Propellant Production

    NASA Technical Reports Server (NTRS)

    Muscatello, A.; Devor, R.; Captain, J.

    2014-01-01

    The multi-NASA center Mars Atmosphere and Regolith COllector/PrOcessor for Lander Operations (MARCO POLO) project was established to build and demonstrate a methaneoxygen propellant production system in a Mars analog environment. Work at the Kennedy Space Center (KSC) Applied Chemistry Laboratory is focused on the Atmospheric Processing Module (APM). The purpose of the APM is to freeze carbon dioxide from a simulated Martian atmosphere containing the minor components nitrogen, argon, carbon monoxide, and water vapor at Martian pressures (approx. 8 torr) by using dual cryocoolers with alternating cycles of freezing and sublimation. The resulting pressurized CO(sub 2) is fed to a methanation subsystem where it is catalytically combined with hydrogen in a Sabatier reactor supplied by the Johnson Space Center (JSC) to make methane and water vapor. We first used a simplified once-through setup and later employed a H(sub 2)CO(sub 2) recycling system to improve process efficiency. This presentation and paper will cover (1) the design and selection of major hardware items, such as the cryocoolers, pumps, tanks, chillers, and membrane separators, (2) the determination of the optimal cold head design and flow rates needed to meet the collection requirement of 88 g CO(sub 2) hr for 14 hr, (3) the testing of the CO(sub 2) freezer subsystem, and (4) the integration and testing of the two subsystems to verify the desired production rate of 31.7 g CH(sub 4) hr and 71.3 g H(sub 2)O hr along with verification of their purity. The resulting 2.22 kg of CH(sub 2)O(sub 2) propellant per 14 hr day (including O(sub 2) from electrolysis of water recovered from regolith, which also supplies the H(sub 2) for methanation) is of the scale needed for a Mars Sample Return mission. In addition, the significance of the project to NASAs new Mars exploration plans will be discussed.

  6. Atmospheric Processing Module for Mars Propellant Production

    NASA Technical Reports Server (NTRS)

    Muscatello, Anthony C.

    2014-01-01

    The multi-NASA center Mars Atmosphere and Regolith COllectorPrOcessor for Lander Operations (MARCO POLO) project was established to build and demonstrate a methaneoxygen propellant production system in a Mars analog environment. Work at the Kennedy Space Center (KSC) Applied Chemistry Laboratory is focused on the Atmospheric Processing Module (APM). The purpose of the APM is to freeze carbon dioxide from a simulated Martian atmosphere containing the minor components nitrogen, argon, carbon monoxide, and water vapor at Martian pressures (8 torr) by using dual cryocoolers with alternating cycles of freezing and sublimation. The resulting pressurized CO(sub 2) is fed to a methanation subsystem where it is catalytically combined with hydrogen in a Sabatier reactor supplied by the Johnson Space Center (JSC) to make methane and water vapor. We first used a simplified once-through setup and later employed a H(sub 2)CO(sub 2) recycling system to improve process efficiency. This presentation and paper will cover (1) the design and selection of major hardware items, such as the cryocoolers, pumps, tanks, chillers, and membrane separators, (2) the determination of the optimal cold head design and flow rates needed to meet the collection requirement of 88 g CO(sub 2) hr for 14 hr, (3) the testing of the CO(sub 2) freezer subsystem, and (4) the integration and testing of the two subsystems to verify the desired production rate of 31.7 g CH(sub 4) hr and 71.3 g H(sub 2)O hr along with verification of their purity. The resulting 2.22 kg of CH(sub 2)O(sub 2) propellant per 14 hr day (including O(sub 2) from electrolysis of water recovered from regolith, which also supplies the H(sub 2) for methanation) is of the scale needed for a Mars Sample Return mission. In addition, the significance of the project to NASAs new Mars exploration plans will be discussed.

  7. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

    NASA Astrophysics Data System (ADS)

    Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

  8. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

    PubMed

    Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ.

  9. Computational Study of the Thermodynamics of Atmospheric Nitration of PAHs via OH-Radical-Initiated Reaction

    NASA Astrophysics Data System (ADS)

    Jariyasopit, N.; Cheong, P.; Simonich, S. L.

    2011-12-01

    Nitrated polycyclic aromatic hydrocarbons (NPAHs) are an important class of PAH derivatives that are more toxic than their parent PAHs (1) and are emitted from direct emission and secondary emission to the atmosphere. The secondary emissions, particularly the OH-radical initiated and NO3-radical-initiated reactions, have been shown to influence the NPAH concentrations in the atmosphere. Gas-phase reactions are thought to be the major sources of NPAHs containing four or fewer rings (2). Besides NPAHs, PAHs lead to a number of other products including oxygenated, hydroxy substituted and ring-opened PAH derivatives (3). For some PAHs, the OH-initiated and NO3-initiated reactions result in the formation of different NPAH isomers, allowing the ratio of these isomers to be used in the determination of direct or secondary emission sources. Previous studies have shown that the PAH gas-phase reactions with OH radical is initiated by the addition of OH radical to the aromatic ring to form hydroxycyclohexadienyl radicals (4). In the presence of NO2, these reactive intermediates readily nitrate with the elimination of water (4). The hydroxycyclohexadienyl-type radical intermediates are also prone to react with other species in the atmosphere or revert back to the original compound (3). The objective of this study was to investigate the thermodynamics of PAH nitration through day-time OH-radical-initiated reactions. The theoretical investigation were carried out using Density Functioanl Theory (B3LYP) and the 6-31G(d) basis set, as implemented in Gaussian03. A number of different PAHs were studied including fluoranthene, pyrene, as well as the molecular weight 302 PAHs such as dibenzo[a,l]pyrene. Computations were also used to predict unknown NPAHs formed by OH-radical-initiated reaction. All intermediates for the OH-radical addition and the following nitration were computed. We have discovered that the thermodynamic stability of the intermediates involved in the PAH

  10. LIF studies of iodine oxide chemistry. Part 3. Reactions IO + NO3 --> OIO + NO2, I + NO3 --> IO + NO2, and CH2I + O2 --> (products): implications for the chemistry of the marine atmosphere at night.

    PubMed

    Dillon, Terry J; Tucceri, María E; Sander, Rolf; Crowley, John N

    2008-03-21

    The technique of pulsed laser photolysis coupled to LIF detection of IO was used to study IO + NO(3) --> OIO + NO(2); I + NO(3) --> (products); CH(2)I + O(2) --> (products); and O((3)P) + CH(2)I(2) --> IO + CH(2)I, at ambient temperature. was observed for the first time in the laboratory and a rate coefficient of k(1 a) = (9 +/- 4) x 10(-12) cm(3) molecule(-1) s(-1) obtained. For , a value of k(2) (298 K) = (1.0 +/- 0.3) x 10(-10) cm(3) molecule(-1) s(-1) was obtained, and a IO product yield close to unity determined. IO was also formed in a close-to-unity yield in , whereas in an upper limit of alpha(3)(IO) < 0.12 was derived. The implications of these results for the nighttime chemistry of the atmosphere were discussed. Box model calculations showed that efficient OIO formation in was necessary to explain field observations of large OIO/IO ratios.

  11. Laser driven hydrogen transfer reactions in atmospheric chemistry

    NASA Astrophysics Data System (ADS)

    Lester, Marsha I.

    2015-03-01

    Ozonolysis of alkenes, an important non-photolytic source of OH radicals in the troposphere, proceeds through energized Criegee intermediates that undergo unimolecular decay to produce OH radicals. In this work, infrared laser activation of cold methyl-substituted Criegee intermediates is utilized to drive hydrogen transfer from the methyl group to the terminal oxygen, followed by dissociation to OH radicals. State-selective excitation of the Criegee intermediates in the CH stretch overtone region combined with sensitive OH detection reveals the infrared spectra of CH3CHOO and (CH3)2 COO, effective barrier heights for the critical hydrogen transfer step, and rapid decay dynamics to OH products. Complementary theory provides insights on the infrared overtone spectra as well as vibrational excitations, structural changes, and energy required to move from the minimum energy configuration of the Criegee intermediates to the transition state for the hydrogen transfer reaction. Research supported by the National Science Foundation.

  12. Atmospheric photosensitized heterogeneous and multiphase reactions: from outdoors to indoors.

    PubMed

    Gómez Alvarez, Elena; Wortham, Henri; Strekowski, Rafal; Zetzsch, Cornelius; Gligorovski, Sasho

    2012-02-21

    This proposal involves direct photolysis processes occurring in the troposphere incorporating photochemical excitation and intermolecular energy transfer. The study of such processes could provide a better understanding of ·OH radical formation pathways in the atmosphere and in consequence, of a more accurate prediction of the oxidative capacity of the atmosphere. Compounds that readily absorb in the tropospheric actinic window (ionic organic complexes, PAHs, aromatic carbonyl compounds) acting as potential photosensitizers of atmospheric relevant processes are explored. The impact of hotosensitation on relevant systems which could act as powerful atmospheric reactors,that is, interface ocean-atmosphere, urban and forest surfaces and indoor air environments is also discussed.

  13. Atmospheric chemistry of benzyl alcohol: kinetics and mechanism of reaction with OH radicals.

    PubMed

    Bernard, François; Magneron, Isabelle; Eyglunent, Grégory; Daële, Véronique; Wallington, Timothy J; Hurley, Michael D; Mellouki, Abdelwahid

    2013-04-02

    The atmospheric oxidation of benzyl alcohol has been investigated using smog chambers at ICARE, FORD, and EUPHORE. The rate coefficient for reaction with OH radicals was measured and an upper limit for the reaction with ozone was established; kOH = (2.8 ± 0.4) × 10(-11) at 297 ± 3 K (averaged value including results from Harrison and Wells) and kO(3) < 2 × 10(-19) cm(3) molecule(-1) s(-1) at 299 K. The products of the OH radical initiated oxidation of benzyl alcohol in the presence of NOX were studied. Benzaldehyde, originating from H-abstraction from the -CH(2)OH group, was identified using in situ FTIR spectroscopy, HPLC-UV/FID, and GC-PID and quantified in a yield of (24 ± 5) %. Ring retaining products originating from OH-addition to the aromatic ring such as o-hydroxybenzylalcohol and o-dihydroxybenzene as well as ring-cleavage products such as glyoxal were also identified and quantified with molar yields of (22 ± 2)%, (10 ± 3)%, and (2.7 ± 0.7)%, respectively. Formaldehyde was observed with a molar yield of (27 ± 10)%. The results are discussed with respect to previous studies and the atmospheric oxidation mechanism of benzyl alcohol.

  14. Aqueous Phase Photo-Oxidation of Succinic Acid: Changes in Hygroscopic Properties and Reaction Products

    NASA Astrophysics Data System (ADS)

    Hudson, P. K.; Ninokawa, A.; Hofstra, J.; de Lijser, P.

    2013-12-01

    Atmospheric aerosol particles have been identified as important factors in understanding climate change. The extent to which aerosols affect climate is determined, in part, by hygroscopic properties which can change as a result of atmospheric processing. Dicarboxylic acids, components of atmospheric aerosol, have a wide range of hygroscopic properties and can undergo oxidation and photolysis reactions in the atmosphere. In this study, the hygroscopic properties of succinic acid aerosol, a non-hygroscopic four carbon dicarboxylic acid, were measured with a humidified tandem differential mobility analyzer (HTDMA) and compared to reaction products resulting from the aqueous phase photo-oxidation reaction of hydrogen peroxide and succinic acid. Reaction products were determined and quantified using gas chromatography-flame ionization detection (GC-FID) and GC-mass spectrometry (GC-MS) as a function of hydrogen peroxide:succinic acid concentration ratio and photolysis time. Although reaction products include larger non-hygroscopic dicarboxylic acids (e.g. adipic acid) and smaller hygroscopic dicarboxylic acids (e.g. malonic and oxalic acids), comparison of hygroscopic growth curves to Zdanovskii-Stokes-Robinson (ZSR) predictions suggests that the hygroscopic properties of many of the product mixtures are largely independent of the hygroscopicity of the individual components. This study provides a framework for future investigations to fully understand and predict the role of chemical reactions in altering atmospheric conditions that affect climate.

  15. Reactions of volatile organic compounds in the atmosphere: Ozone-alkene reactions

    NASA Astrophysics Data System (ADS)

    Fenske, Jill Denise

    2000-08-01

    Photochemical smog cannot form without sunlight, nitrogen oxides, and volatile organic compounds (VOC). This dissertation addresses several different aspects of VOC chemistry in the atmosphere. Aside from ambient levels of VOC outdoors, VOC are also present at moderate concentrations indoors. Many studies have measured indoor air concentrations of VOC, but only one considered the effects of human breath. The major VOC in the breath of healthy individuals are isoprene (12-580 ppb), acetone (1.2-1800 ppb), ethanol (13-1000 ppb), methanol (160-2000 ppb), and other alcohols. Human emissions of VOC are negligible on a regional (less than 4%) and global scale (less than 0.3%). However, in indoor air, under fairly crowded situations, human emissions of VOC may dominate other sources of VOC. An important class of VOC in the atmosphere is alkenes, due to their high reactivity. The ozone reaction with alkenes forms OH radicals, a powerful oxidizing agent in the troposphere. OH radical formation yields from the ozonolysis of several cycloalkenes were measured using small amounts of fast-reacting aromatics and aliphatic ethers to trace OH formation. The values are 0.62 +/- 0.15, 0.54 +/- 0.13, 0.36 +/- 0.08, and 0.91 +/- 0.20 for cyclopentene, cyclohexene, cycloheptene and 1-methylcyclohexene, respectively. Density functional theory calculations at the B3LYP/6-31 G(d,p) level are presented to aid in understanding the trends observed. The pressure dependence of OH radical yields may lend insight into the formation mechanism. We have made the first study of the pressure dependence of the OH radical yield for ethene, propene, 1-butene, trans-2-butene, and 2,3-dimethyl-2- butene over the range 20-760 Torr, and trans -3-hexene, and cyclopentene over the range 200-760 Torr. The OH yields from ozonolysis of ethene and propene were pressure dependent, while the other compounds had OH yields that were independent of pressure. Ozone-alkene reactions form vibrationally excited carbonyl

  16. Reactions of Atmospheric Particulate Stabilized Criegee Intermediates Lead to High-Molecular-Weight Aerosol Components.

    PubMed

    Wang, MingYi; Yao, Lei; Zheng, Jun; Wang, XinKe; Chen, JianMin; Yang, Xin; Worsnop, Douglas R; Donahue, Neil M; Wang, Lin

    2016-06-07

    Aging of organic aerosol particles is one of the most poorly understood topics in atmospheric aerosol research. Here, we used an aerosol flow tube together with an iodide-adduct high-resolution time-of-flight chemical-ionization mass spectrometer equipped with a Filter Inlet for Gases and AEROsols (FIGAERO-HRToF-CIMS) to investigate heterogeneous ozonolysis of oleic acid (OL), developing a comprehensive oxidation mechanism with observed products. In addition to the well-known first-generation C9 products including nonanal, nonanoic acid, azelaic acid, and 9-oxononanoic acid, the iodide-adduct chemical ionization permitted unambiguous determination of a large number of high-molecular-weight particulate products up to 670 Da with minimum amounts of fragmentation. These high-molecular-weight products are characterized by a fairly uniform carbon oxidation state but stepwise addition of a carbon backbone moiety, and hence continuous decrease in the volatility. Our results demonstrate that heterogeneous oxidation of organic aerosols has a significant effect on the physiochemical properties of organic aerosols and that reactions of particulate SCIs from ozonolysis of an unsaturated particulate species represent a previously underappreciated mechanism that lead to formation of high-molecular-weight particulate products that are stable under typical atmospheric conditions.

  17. Assessment of reaction-rate predictions of a collision-energy approach for chemical reactions in atmospheric flows.

    SciTech Connect

    Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert

    2010-06-01

    A recently proposed approach for the Direct Simulation Monte Carlo (DSMC) method to calculate chemical-reaction rates is assessed for high-temperature atmospheric species. The new DSMC model reproduces measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular properties, the new model is inherently able to predict reaction rates for arbitrary non-equilibrium conditions. DSMC non-equilibrium reaction rates are compared to Park's phenomenological nonequilibrium reaction-rate model, the predominant model for hypersonic-flow-field calculations. For near-equilibrium conditions, Park's model is in good agreement with the DSMC-calculated reaction rates. For far-from-equilibrium conditions, corresponding to a typical shock layer, significant differences can be found. The DSMC predictions are also found to be in very good agreement with measured and calculated non-equilibrium reaction rates, offering strong evidence that this is a viable and reliable technique to predict chemical reaction rates.

  18. Reaction mechanism and rheological properties of polypropylene irradiated under various atmospheres

    NASA Astrophysics Data System (ADS)

    Lugão, Ademar B.; Hutzler, Beatriz; Ojeda, Telmo; Tokumoto, Shinichi; Siemens, Richard; Makuuchi, Keizo; Villavicencio, Anna.-Lucia C. H.

    2000-03-01

    It is well-known that the melt-strength properties of a polymer increases with molecular weight and with long chain branching due to the increase in the entanglement level. This study is a contribution for the understanding of the following points: — the role of branching, crosslinking and degradation on melt strength properties; — the mechanism and the kinetics of PP irradiation with time of irradiation and the importance of double bond formation. The results showed that degradation was the major reaction in the initial step of irradiation no matter the atmosphere and or antioxidant. However, double bond formation increased the production of branching and crosslinking reactions. Double bond formation had no effect on the crystallization kinetics, on the other hand, long chain branching had a marked effect on the crystallization temperature.

  19. The reaction of the atmosphere to solar disturbances

    NASA Technical Reports Server (NTRS)

    Mikhnevich, V. V.

    1979-01-01

    The effect of solar flares on the thermosphere and the troposphere is investigated. It is found that during periods of geoeffect solar disturbances, there is a connection between phenomena in the upper and lower atmospheres and that variations in atmospheric parameters correlate with changes in the geomagnetic index.

  20. The OH-initiated atmospheric chemical reactions of polyfluorinated dibenzofurans and polychlorinated dibenzofurans: A comparative theoretical study.

    PubMed

    Zeng, Xiaolan; Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

    2017-02-01

    The atmospheric chemical reactions of some polyfluorinated dibenzofurans (PFDFs) and polychlorinated dibenzofurans (PCDFs), initiated by OH radical, were investigated by performing theoretical calculations using density functional theory (DFT) and B3LYP/6-311++G(2df,p) method. The obtained results indicate that OH addition reactions of PFDFs and PCDFs occurring at C1∼4 and CA sites are thermodynamic spontaneous changes and the branching ratio of the PF(C)DF-OH adducts is decided primarily by kinetic factor. The OH addition reactions of PFDFs taking place at fluorinated C1∼4 positions are kinetically comparable with those occurring at nonfluorinated C1∼4 positions, while OH addition reactions of PCDFs occurring at chlorinated C1∼4 sites are negligible. The total rate constants of the addition reactions of PFDFs or PCDFs become smaller with consecutive fluorination or chlorination, and substituting at C1 position has more adverse effects than substitution at other sites. The succedent O2 addition reactions of PF(C)DF-OH adducts are thermodynamic nonspontaneous processes under the atmospheric conditions, and have high Gibbs free energies of activation (ΔrG(≠)). The substituted dibenzofuranols are the primary oxidation products for PCDFs under the atmospheric conditions. However, other oxidative products may also be available for PFDFs besides substituted dibenzofuranols.

  1. Mineral reaction buffering of Venus' atmosphere: A thermochemical constraint and implications for Venus-like planets

    NASA Astrophysics Data System (ADS)

    Treiman, Allan H.; Bullock, Mark A.

    2012-02-01

    The equilibrium suggested as a buffer for CO 2 in the Venus atmosphere, CaCO 3 + SiO 2 = CaSiO 3 + CO 2, cannot act as a buffer at the Venus surface/troposphere - the pressure-temperature slope of the equilibrium and that of the atmosphere (dry adiabat with significant greenhouse heating) do not provide buffering capacity (if indeed CaCO 3 were present). Instead, perturbations to T or P(CO 2) can produce catastrophic expansion or collapse of the atmosphere. This instability can be generalized to all devolatilization reactions that produce a radiatively active gas in a planetary atmosphere dominated by such gases, and gives a simple thermochemical criterion for whether a reaction could buffer such an atmosphere. Simple decarbonation reactions fail this criterion, suggesting that the abundance of CO 2 in a CO 2-dominated atmosphere cannot be buffered by chemical reactions with the surface; a similar conclusion holds for the abundance of H 2O in an H 2O-dominated (steam) atmosphere. Buffering of minor gases is more likely; a mineral buffer equilibrium for SO 2 proposed for Venus, FeS 2 + CO 2 = Fe 3O 4 + SO 2 + CO, passes the thermochemical criterion, as does a reaction involving Ca sulfate. These inferences can be generalized to atmospheres in 'moist' adiabatic equilibria, and to extrasolar Venus-like planets, and will help in interpreting the compositions of their atmospheres.

  2. Ion transport of Fr nuclear reaction products

    SciTech Connect

    Behr, J.A.; Cahn, S.B.; Dutta, S.B.

    1993-04-01

    Experiments planned for fundamental studies of radioactive atoms in magneto-optic traps require efficient deceleration and transport of nuclear reaction products to energies and locations where they can be trapped. The authors have built a low-energy ion transport system for Francium and other alkalis. A thick Au target is held on a W rod at 45{degrees} to the accelerator beam direction. The heavy-ion fusion reaction 115 MeV {sup 18}O + {sup 197}Au produces {sup 211,210,209}Fr recoil products which are stopped in the target. The target is heated to close to the melting point of Au to allow the Fr to diffuse to the surface, where it is ionized due to Au`s high work function, and is directly extracted by an electrode at 90{degrees} to the accelerator beam direction. The Fr is transported by electrostatic optics {approximately}1 m to a catcher viewed by an {alpha} detector: {ge}15% of the Fr produced in the target reaches the catcher. 2{times}10{sup 5} Fr/sec have been produced at the catcher, yielding at equilibrium a sample of 3x10{sup 7}Fr nuclei. This scheme physically decouples the target diffusion from the surface neutralization process, which can occur at a lower temperature more compatible with the neutral-atom trap.

  3. Feasibility Study of Venus Surface Cooling Using Chemical Reactions with the Atmosphere

    NASA Technical Reports Server (NTRS)

    Evans, Christopher

    2013-01-01

    A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options.

  4. Feasibility Study of Venus Surfuce Cooling Using Chemical Reactions with the Atmosphere

    NASA Technical Reports Server (NTRS)

    Evans, Christopher

    2013-01-01

    A literature search and theoretical analysis were conducted to investigate the feasibility of cooling a craft on Venus through chemical reformation of materials from the atmosphere. The core concept was to take carbon dioxide (CO2) from the Venus atmosphere and chemically reform it into simpler compounds such as carbon, oxygen, and carbon monoxide. This process is endothermic, taking energy from the surroundings to produce a cooling effect. A literature search was performed to document possible routes for achieving the desired reactions. Analyses indicated that on Venus, this concept could theoretically be used to produce cooling, but would not perform as well as a conventional heat pump. For environments other than Venus, the low theoretical performance limits general applicability of this concept, however this approach to cooling may be useful in niche applications. Analysis indicated that environments with particular atmospheric compositions and temperatures could allow a similar cooling system to operate with very good performance. This approach to cooling may also be useful where the products of reaction are also desirable, or for missions where design simplicity is valued. Conceptual designs for Venus cooling systems were developed using a modified concept, in which an expendable reactant supply would be used to promote more energetically favorable reactions with the ambient CO2, providing cooling for a more limited duration. This approach does not have the same performance issues, but the use of expendable supplies increases the mass requirements and limits the operating lifetime. This paper summarizes the findings of the literature search and corresponding analyses of the various cooling options

  5. ENVIRONMENTAL CHAMBER STUDIES OF MERCURY REACTIONS IN THE ATMOSPHERE

    EPA Science Inventory

    Mercury is released into the environment through both natural and anthropogenic pathways. The cycling and fate of mercury in atmospheric, soil, and water ecosystems is impacted by various factors, including chemical transformation and transport. An understanding of these proces...

  6. ENVIRONMENTAL CHAMBER STUDIES OF MERCURY REACTIONS IN THE ATMOSPHERE

    EPA Science Inventory

    Mercury is released into the environment through both natural and anthropogenic pathways. The cycling and fate of mercury in atmospheric, soil, and water ecosystems is impacted by various factors, including chemical transformation and transport. An understanding of these proces...

  7. Assessment and Requirements of Nuclear Reaction Databases for GCR Transport in the Atmosphere and Structures

    NASA Technical Reports Server (NTRS)

    Cucinotta, F. A.; Wilson, J. W.; Shinn, J. L.; Tripathi, R. K.

    1998-01-01

    The transport properties of galactic cosmic rays (GCR) in the atmosphere, material structures, and human body (self-shielding) am of interest in risk assessment for supersonic and subsonic aircraft and for space travel in low-Earth orbit and on interplanetary missions. Nuclear reactions, such as knockout and fragmentation, present large modifications of particle type and energies of the galactic cosmic rays in penetrating materials. We make an assessment of the current nuclear reaction models and improvements in these model for developing required transport code data bases. A new fragmentation data base (QMSFRG) based on microscopic models is compared to the NUCFRG2 model and implications for shield assessment made using the HZETRN radiation transport code. For deep penetration problems, the build-up of light particles, such as nucleons, light clusters and mesons from nuclear reactions in conjunction with the absorption of the heavy ions, leads to the dominance of the charge Z = 0, 1, and 2 hadrons in the exposures at large penetration depths. Light particles are produced through nuclear or cluster knockout and in evaporation events with characteristically distinct spectra which play unique roles in the build-up of secondary radiation's in shielding. We describe models of light particle production in nucleon and heavy ion induced reactions and make an assessment of the importance of light particle multiplicity and spectral parameters in these exposures.

  8. A computational study of acid catalyzed aerosol reactions of atmospherically relevant epoxides.

    PubMed

    Piletic, Ivan R; Edney, Edward O; Bartolotti, Libero J

    2013-11-07

    Epoxides are important intermediates of atmospheric isoprene oxidation. Their subsequent reactions in the particle phase lead to the production of organic compounds detected in ambient aerosols. We apply density functional theory to determine the important kinetic factors that drive epoxide reactions in the particle phase. Specifically, the importance of acid catalysis and solvent polarity are investigated using a variety of epoxides and nucleophiles. The condensed phase is modeled using molecular clusters immersed in a dielectric continuum and a majority of the calculations are performed with the M062x density functional and the 6-311++G** basis set. Calculations of acid catalyzed epoxide hydrolysis transition states for simple primary, secondary and tertiary epoxides are consistent with an A-2 mechanism where the nucleophile (water) interacts with an epoxide carbon in the transition state. By applying transition state theory to this mechanism, the overall rate constants of epoxide reactions such as hydrolysis, organosulfate formation, organonitrate formation and oligomerization are determined. The calculations indicate that the acid catalyzed hydrolysis rate constant of 2-methyl-2,3-epoxybutane-1,4-diol (β-IEPOX--an isoprene epoxide produced under low NOx conditions) is approximately 30 times greater than 2-methyl-2,3-epoxypropanoic acid (MAE--methacrylic acid epoxide derived from isoprene and produced at high NOx concentrations). Furthermore, acid catalyzed organosulfate formation and epoxide oligomerization reactions are competitive and appear to be kinetically favorable over the hydrolysis of IEPOX.

  9. Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

    PubMed

    Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

    2014-05-22

    Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P < 10 Torr with the high pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

  10. Transfer-type products accompanying cold fusion reactions

    SciTech Connect

    Adamian, G.G.; Antonenko, N.V.

    2005-12-15

    Production of nuclei heavier than the target is treated for projectile-target combinations used in cold fusion reactions leading to superheavy nuclei. These products are related to transfer-type or to asymmetry-exit-channel quasifission reactions. The production of isotopes in the transfer-type reactions emitting of {alpha} particles with large energies is discussed.

  11. Kinetics of the photolysis and OH reaction of 4-hydroxy-4-methyl-2-pentanone: Atmospheric implications

    NASA Astrophysics Data System (ADS)

    Aslan, L.; Laversin, H.; Coddeville, P.; Fittschen, C.; Roth, E.; Tomas, A.; Chakir, A.

    2017-02-01

    This study provides the first kinetic and mechanistic study of the photolysis of 4-hydroxy-4-methyl-2-pentanone (4H4M2P) and the determination of the temperature dependence of the relative rate coefficient for the reaction of OH radicals with 4H4M2P. The UV absorption spectrum of 4H4M2P was determined in the spectral range 200-360 nm. The photolysis frequency of this compound in the atmosphere was evaluated relative to actinometers and found to be J4 H 4M 2 P atm = 4.2 ×10-3h-1 , corresponding to a lifetime of about 10 days. Using 4H4M2P cross section measurements, an atmospheric effective quantum yield of 0.15 was calculated. The main primary photolysis products were acetone (121 ± 4) % and formaldehyde (20 ± 1) %. A low methanol yield of (3.0 ± 0.3) % was also determined. These results enabled us to propose a mechanistic scheme for the photolysis. Rate coefficients for the reaction of 4H4M2P with OH radicals were determined over the temperature range 298-354 K and the following Arrhenius expression was obtained: kOH+4M4H2P = (1.12 ± 0.40) × 10-12exp(461.5 ± 60/T) cm3 molecule-1 s-1. The lifetimes of 4H4M2P due to reaction with OH radicals has been estimated to ∼2.5 days and indicates that the gas-phase reaction with the OH could be the main loss process for this compound.

  12. Atmospheric fate of methyl vinyl ketone: peroxy radical reactions with NO and HO2.

    PubMed

    Praske, Eric; Crounse, John D; Bates, Kelvin H; Kurtén, Theo; Kjaergaard, Henrik G; Wennberg, Paul O

    2015-05-14

    First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl peroxy R2a , (2) a hydroperoxide R2b , and (3) an α-diketone R2c . The α-diketone likely results from HOx-neutral chemistry previously only known to occur in reactions of HO2 with halogenated peroxy radicals. Quantum chemical calculations demonstrate that all channels are kinetically accessible at 298 K. In the high NO chemistry, glycolaldehyde is produced with a yield of 74 ± 6.0%. Two alkyl nitrates are formed with a combined yield of 4.0 ± 0.6%. We revise a three-dimensional chemical transport model to assess what impact these modifications in the MVK mechanism have on simulations of atmospheric oxidative chemistry. The calculated OH mixing ratio over the Amazon increases by 6%, suggesting that the low NO chemistry makes a non-negligible contribution toward sustaining the atmospheric radical pool.

  13. Production of pesticide metabolites by oxidative reactions.

    PubMed

    Hodgson, E

    1982-08-01

    The cytochrome P-450-dependent monooxygenase system catalyzes a wide variety of oxidations of pesticide chemicals and related compounds. These reactions include epoxidation and aromatic hydroxylation, aliphatic hydroxylation, O-, N- and S-dealkylation, N-oxidation, oxidative deamination, S-oxidation, P-oxidation, desulfuration and ester cleavage and may result in either detoxication or activation of the pesticide. The current status of such reactions, relative to the production, in vivo, of biologically active intermediates in pesticide metabolism is summarized. More recently we have shown that the FAD-containing monooxygenase of mammalian liver (E.C.1.14.13.8), a xenobiotic metabolizing enzyme of broad specificity formerly known as an amine oxidase, is involved in a variety of pesticide oxidations. These include sulfoxidation of organophosphorus insecticides such as phorate and disulfoton, oxidative desulfuration of phosphonate insecticides such as fonofos and oxidation at the phosphorus atom in such compounds as the cotton defoliant, folex. The relative importance of the FAD-containing monooxygenase vis-a-vis the cytochrome P-450-dependent monooxygenase system is discussed, based on in vitro studies on purified enzymes.

  14. Reactions of uranium hexafluoride photolysis products

    NASA Astrophysics Data System (ADS)

    Lyman, John L.; Laguna, Glenn; Greiner, N. R.

    1985-01-01

    This paper confirms that the ultraviolet photolysis reactions of UF6 in the B band spectral region is simple bond cleavage to UF5 and F. The photolysis products may either recombine to UF6 or the UF5 may dimerize, and ultimately polymerize, to solid UF5 particles. We use four methods to set an upper limit for the rate constant for recombination of kr<2.0×10-12cm3 molecule-1 s-1. We measure the rate constant for UF5 dimerization to be kd=(1.0±0.2)×10-11 cm3 molecule-1 s-1. The principal method employed in these studies is the use of diode lasers to monitor, in real time, the changes in density of the species UF6 and UF5 after laser photolysis of the UF6 gas sample.

  15. Gas-phase reactions of halogen species of atmospheric importance

    NASA Astrophysics Data System (ADS)

    Heard, Anne C.

    A low-pressure discharge-flow technique, with various optical detection methods, has been used to determine bimolecular rate coefficients for a number of reactions in the gas-phase between OH radicals and organic halogen-containing molecules and between NO3 radicals and the iodine species I2 and I. These experiments have shown that: (1) the reaction of methyl iodide with OH accounts for approximately 2 percent of the removal of CH3I from the troposphere as compared with photolysis; (2) abstraction of I-atoms from a C-I bond by OH is probable in the gas-phase; (3) the halogen-containing anaesthetic substances halothane CF3CClBrH, enflurane CF2HOCF2CFClH, isoflurane CF2HOCClHCF3 and sevoflurane (CF3)2CHOCFH2 have significantly shorter tropospheric lifetimes than the fully halogenated CFCs and halons because of reaction with the OH radical and are thus unlikely to be transported up to the stratosphere where they could contribute to the depletion of ozone. Data obtained for reactions between OH and some 'CFC alternatives' along with measurements of the integrated absorption cross-sections of the compounds in the spectral region 800-1200 cm(exp -1) were used to calculate ozone depletion potentials (ODP) and greenhouse warming potentials relative to CFCl3 for each compound. The study of the reactions between OH and CF3CFBrH and CF2BrH was used to provide a useful first estimate of the environmental acceptability of these compounds in the context of their possible use as replacements for the conventional CFCs. A method was developed to provide a first estimate of the ODP of a halogenated alkane without use of a complicated (and expensive) computer modeling scheme. A reaction between molecular iodine and the nitrate radical in the gas-phase was discovered and the kinetics of this reaction have been studied. No temperature or pressure dependence was observed for the rate of reaction, the rate constant of which was found to be (1.5 +/- 0.5) x 10(exp -12)/cu cm

  16. Kinetics of Thermochemical Reactions Important in the Venus Atmospheric Sulfur Cycle

    NASA Technical Reports Server (NTRS)

    Fegley, Bruce, Jr.

    1997-01-01

    The purpose of this project was to experimentally measure the rates of several thermochemical gas-solid reactions between sulfur gases in the Venus atmosphere and reactive minerals on the hot Venus surface. Despite the great importance of these reactions for the maintenance of significant amounts of sulfur gases (and thus for the maintenance of the global cloud cover) in the atmosphere of Venus, essentially no kinetic data are currently available for them.

  17. Photochemical production of formaldehyde in earth's primitive atmosphere

    NASA Technical Reports Server (NTRS)

    Pinto, J. P.; Gladstone, G. R.; Yung, Y. L.

    1980-01-01

    Formaldehyde could have been produced by photochemical reactions in the earth's primitive atmosphere, at a time when it consisted mainly of molecular nitrogen, water vapor, carbon dioxide, and trace amounts of molecular hydrogen and carbon monoxide. Removal of formaldehyde from the atmosphere by precipitation can provide a source of organic carbon to the oceans at the rate of 100 billion moles per year. Subsequent reactions of formaldehyde in primeval aquatic environments would have implications for the abiotic synthesis of complex organic molecules and the origin of life.

  18. Photochemical production of formaldehyde in earth's primitive atmosphere

    NASA Technical Reports Server (NTRS)

    Pinto, J. P.; Gladstone, G. R.; Yung, Y. L.

    1980-01-01

    Formaldehyde could have been produced by photochemical reactions in the earth's primitive atmosphere, at a time when it consisted mainly of molecular nitrogen, water vapor, carbon dioxide, and trace amounts of molecular hydrogen and carbon monoxide. Removal of formaldehyde from the atmosphere by precipitation can provide a source of organic carbon to the oceans at the rate of 100 billion moles per year. Subsequent reactions of formaldehyde in primeval aquatic environments would have implications for the abiotic synthesis of complex organic molecules and the origin of life.

  19. Kinetics of OH + CO reaction under atmospheric conditions

    NASA Technical Reports Server (NTRS)

    Hynes, A. J.; Wine, P. H.; Ravishankara, A. R.

    1986-01-01

    A pulsed laser photolysis-pulsed laser-induced fluorescence technique is used to directly measure the temperature, pressure, and H2O concentration dependence on k1 in air. K1 is found to increase linearly with increasing pressure at pressures of not greater than 1 atm, and the pressure dependence of k1 at 299 K is the same in N2 buffer gas as in O2 buffer gas. The rate constant in the low-pressure limit and the slope of the k1 versus pressure dependence are shown to be the same at 262 K as at 299 K. The present results significantly reduce the current atmospheric model uncertainties in the temperature dependence under atmospheric conditions, in the third body efficiency of O2, and in the effect of water vapor on k1.

  20. Nitrogen-Containing Low Volatile Compounds from Pinonaldehyde-Dimethylamine Reaction in the Atmosphere: A Laboratory and Field Study.

    PubMed

    Duporté, Geoffroy; Parshintsev, Jevgeni; Barreira, Luís M F; Hartonen, Kari; Kulmala, Markku; Riekkola, Marja-Liisa

    2016-05-03

    Pinonaldehyde, which is among the most abundant oxidation products of α-pinene, and dimethylamine were selected to study the formation of N-containing low volatile compounds from aldehyde-amine reactions in the atmosphere. Gas phase reactions took place in a Tedlar bag, which was connected to a mass spectrometer ionization source via a short deactivated fused silica column. In addition to on-line analysis, abundance of gaseous precursors and reaction products were monitored off-line. Condensable products were extracted from the bag's walls with a suitable solvent and analyzed by gas chromatography coupled to chemical ionization high-resolution quadrupole time-of-flight mass spectrometry and by ultra-high-performance liquid chromatography coupled to electrospray ionization Orbitrap mass spectrometry. The reactions carried out resulted in several mid-low vapor pressure nitrogen-containing compounds that are potentially important for the formation of secondary organic aerosols in the atmosphere. Further, the presence of brown carbon, confirmed by liquid chromatography-UV-vis-mass spectrometry, was observed. Some of the compounds identified in the laboratory study were also observed in aerosol samples collected at SMEAR II station (Hyytiälä, Finland) in August 2015 suggesting the importance of aldehyde-amine reactions for the aerosol formation and growth.

  1. Electroweak meson production reaction in the nucleon resonance region

    SciTech Connect

    Sato, Toru

    2015-10-15

    We report on our recent study of the the neutrino-nucleon reaction in the nucleon resonance region. The dynamical reaction model of meson production reaction on the nucleon for the pion and photon induced reaction has been developed in order to investigate the spectrum of nucleon excited state. We have extended this model in order to describe the weak meson production reactions with the πN, ηN, KΛ, KΣ and ππN final states. We also studied the role of the final state interaction in the photon and the neutrino induced pion production reaction on the deuteron around the Δ(1232) resonance region.

  2. The production of trace gases by photochemistry and lightning in the early atmosphere

    NASA Technical Reports Server (NTRS)

    Levine, J. S.; Tennille, G. M.; Towe, K. M.; Khanna, R. K.

    1986-01-01

    Recent atmospheric calculation suggest that the prebiological atmosphere was most probably composed of nitrogen, carbon dioxide, and water vapor, resulting from volatile outgassing, as opposed to the older view of a strongly reducing early atmosphere composed of methane, ammonia, and hydrogen. Photochemical calculations indicate that methane would have been readily destroyed via reaction with the hydroxyl radical produced from water vapor and that ammonia would have been readily lost via photolysis and rainout. The rapid loss of methane and ammonia, coupled with the absence of a significant source of these gases, suggest that atmospheric methane and ammonia were very short lived, if they were present at all. An early atmosphere of N2, CO2, and H2O is stable and leads to the chemical production of a number of atmospheric species of biological significance, including oxygen, ozone, carbon monoxide, formaldehyde, and hydrogen cyanide. Using a photochemical model of the early atmosphere, the chemical productionof these species over a wide range of atmospheric parameters were investigated. These calculations indicate that early atmospheric levels of O3 were significantly below the levels needed to provide UV shielding. The fate of volcanically emitted sulfur species, e.g., sulfur dioxide and hydrogen sulfide, was investigated in the early atmosphere to assess their UV shielding properties. The photochemical calculations show that these species were of insufficient levels, due in part to their short photochemical lifetimes, to provide UV shielding.

  3. The production of trace gases by photochemistry and lightning in the early atmosphere

    NASA Technical Reports Server (NTRS)

    Levine, J. S.; Tennille, G. M.; Towe, K. M.; Khanna, R. K.

    1986-01-01

    Recent atmospheric calculation suggest that the prebiological atmosphere was most probably composed of nitrogen, carbon dioxide, and water vapor, resulting from volatile outgassing, as opposed to the older view of a strongly reducing early atmosphere composed of methane, ammonia, and hydrogen. Photochemical calculations indicate that methane would have been readily destroyed via reaction with the hydroxyl radical produced from water vapor and that ammonia would have been readily lost via photolysis and rainout. The rapid loss of methane and ammonia, coupled with the absence of a significant source of these gases, suggest that atmospheric methane and ammonia were very short lived, if they were present at all. An early atmosphere of N2, CO2, and H2O is stable and leads to the chemical production of a number of atmospheric species of biological significance, including oxygen, ozone, carbon monoxide, formaldehyde, and hydrogen cyanide. Using a photochemical model of the early atmosphere, the chemical productionof these species over a wide range of atmospheric parameters were investigated. These calculations indicate that early atmospheric levels of O3 were significantly below the levels needed to provide UV shielding. The fate of volcanically emitted sulfur species, e.g., sulfur dioxide and hydrogen sulfide, was investigated in the early atmosphere to assess their UV shielding properties. The photochemical calculations show that these species were of insufficient levels, due in part to their short photochemical lifetimes, to provide UV shielding.

  4. Influence of reaction atmosphere and solvent on biochar yield and characteristics.

    PubMed

    Marx, S; Chiyanzu, I; Piyo, N

    2014-07-01

    Sunflower husks were converted to biochar via thermochemical liquefaction in different solvents and reaction atmospheres. Highest biochar yields obtained was 574 g kg(-1) husks. Surface area of the produced chars and evolution of aromatic compounds in the biochar structure increased with an increase in temperature. Volatile matter and N-content decreased and S-content decreased significantly with an increase in temperature which is favourable should the biochars be used for combustion. The HHV of the biochars were significantly higher than that of the feedstock as was also indicated by the energy densification ratio. The biochars compared favourable with coal on a Van Krevelen diagram, showing the possibility of the biochars for application in co-gasification. CO2 performed better in retaining the energy of the feedstock in the biochar (up to 58%). It was shown that sunflower husks are a viable feedstock for the production of biochars for application in co-gasification or combustion.

  5. Gas-Phase Reactions of Halogen Species of Atmospheric Importance.

    NASA Astrophysics Data System (ADS)

    Heard, Anne C.

    Available from UMI in association with The British Library. Requires signed TDF. A low-pressure discharge-flow technique, with various optical detection methods, has been used to determine bimolecular rate coefficients for a number of reactions in the gas-phase between OH radicals and organic halogen -containing molecules and between NO_3 radicals and the iodine species I_2 and I. These experiments have shown that: (i) the reaction of methyl iodide with OH accounts for approximately 2% of the removal of CH_3I from the troposphere as compared with photolysis; (ii) abstraction of I-atoms from a C-I bond by OH is probable in the gas -phase; (iii) the halogen-containing anaesthetic substances halothane CF_3CCl BrH, enflurane CF_2HOCF _2CFClH, isoflurane CF_2HOCClHCF _3 and sevoflurane (CF_3) _2CHOCFH_2 have significantly shorter tropospheric lifetimes than the fully halogenated CFCs and halons because of reaction with the OH radical and are thus unlikely to be transported up to the stratosphere where they could contribute to the depletion of ozone. Data obtained for reactions between OH and some 'CFC alternatives' along with measurements of the integrated absorption cross -sections of the compounds in the spectral region 800-1200 cm^{-1} were used to calculate ozone depletion potentials (ODP) and greenhouse warming potentials relative to CFCl_3 for each compound. The study of the reactions between OH and CF_3CFBrH and CF _2BrH was used to provide a useful first estimate of the environmental acceptability of these compounds in the context of their possible use as replacements for the conventional CFCs. A method was developed to provide a first estimate of the ODP of a halogenated alkane without use of a complicated (and expensive) computer modeling scheme. A reaction between molecular iodine and the nitrate radical in the gas-phase was discovered and the kinetics of this reaction have been studied. No temperature or pressure dependence was observed for the rate of

  6. Formaldehyde Reactions with Amines and Ammonia: Particle Formation and Product Identification

    NASA Astrophysics Data System (ADS)

    Galloway, M. M.; Millage, K. D.; Rodriguez, A.; Sedehi, N.; Powelson, M. H.; De Haan, D. O.

    2012-12-01

    Aqueous phase reactions between carbonyls and amines or ammonium salts have recently been implicated in secondary organic aerosol and brown carbon formation processes. Formaldehyde is ubiquitous in the atmosphere, and is present in both the gas and aqueous phases. However, the reactions of formaldehyde in the aqueous phase have not been completely characterized. This study aims to determine the interactions between formaldehyde and amines or ammonium salts present in atmospheric droplets. Bulk phase reactions of formaldehyde with these reactive nitrogen-containing compounds were monitored with ESI-MS and NMR to determine reaction kinetics and for product characterization, while UV-Vis spectroscopy was used to monitor changes in light absorption over time. Hexamethylenetetramine was found to be a major product of the formaldehyde/ammonium sulfate reaction, appearing within minutes of mixing. No products were formed that absorbed light beyond 225 nm. Mono-disperse particles containing mixtures of formaldehyde and ammonium sulfate or an amine were dried and analyzed via SMPS to determine the non-volatile fraction of the reaction products. Similarly, aqueous droplets were dried in a humid atmosphere to determine residual aerosol sizes over time as a function of formaldehyde concentration. This work indicates that formaldehyde plays a key role in aqueous-phase organic processing, as it has been observed to contribute to both an increase and reduction in the diameter and volume of residual aerosol particles.

  7. Secondary Organic Aerosol Formation by Molecular-Weight Building Reactions of Biogenic Oxidation Products

    NASA Astrophysics Data System (ADS)

    Barsanti, K.; Guenther, A.; Matsunaga, S.; Smith, J.

    2006-12-01

    Understanding the chemical composition of atmospheric organic aerosols (OA) remains one of the significant challenges to accurately representing OA in air quality and climate models. Meeting this challenge will require further understanding of secondary organic aerosols (SOA), of which biogenic emissions are thought to be major precursors. Of recent interest is the significance of higher-molecular weight (MW) compounds (i.e., "oligomers"). Theoretical, laboratory, and field study results suggest that relatively volatile oxidation products may contribute to SOA formation through multi-phase MW- building reactions. The significance of such reactions for biogenic SOA formation, including for newly considered precursors such as isoprene, is explored in this work. Theoretical and field studies are employed to: 1) identify MW-building reactions that may contribute to SOA formation in the atmosphere, 2) identify MW-building reaction products in ambient samples, and 3) parameterize atmospheric SOA formation by MW-building reactions of biogenic oxidation products. Likely reactions of biogenic oxidation products include ester, amide, and peroxyhemiacetal formation. Each of the proposed reactions involves known oxidation productions of biogenic precursors (e.g., carboxylic acids and aldehydes) reacting with one another and/or other atmospheric constituents (e.g., sulfuric acid and ammonia) to form higher-MW/lower-volatility products that can condense to form SOA. It has been suggested that products of MW-building reactions can revert to the parent reactants during sampling and analysis. Thus, relatively volatile compounds detected in ambient particle samples in fact may be decomposition products of higher-MW products. The contribution of relatively volatile biogenic oxidation products to SOA via ester, amide, and peroxyhemiacetal formation, as determined by studies based on fundamental thermodynamics and gas/particle partitioning theory, will be discussed; in addition to

  8. Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions.

    PubMed

    Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

    2017-07-01

    Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO3) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO3-nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO3) was produced in the flame. The HNO3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO3 showed the strongest affinity to histidine and formed (Mhistidine-H+HNO3)(-) complex ions, whereas some amino acids did not react with HNO3 at all. Reactions between HNO3 and histidine residues in AI and AII resulted in the formation of dominant [MAI-H+(HNO3)](-) and [MAII-H+(HNO3)](-) ions. Results from analyses of AAs and insulin indicated that HNO3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO3)n](3-) complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins. Graphical Abstract ᅟ.

  9. Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions

    NASA Astrophysics Data System (ADS)

    Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

    2017-07-01

    Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO3) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO3-nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO3) was produced in the flame. The HNO3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO3 showed the strongest affinity to histidine and formed (Mhistidine-H+HNO3)- complex ions, whereas some amino acids did not react with HNO3 at all. Reactions between HNO3 and histidine residues in AI and AII resulted in the formation of dominant [MAI-H+(HNO3)]- and [MAII-H+(HNO3)]- ions. Results from analyses of AAs and insulin indicated that HNO3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO3)n]3- complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins.

  10. Molecule-based approach for computing chemical-reaction rates in upper atmosphere hypersonic flows.

    SciTech Connect

    Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert

    2009-08-01

    This report summarizes the work completed during FY2009 for the LDRD project 09-1332 'Molecule-Based Approach for Computing Chemical-Reaction Rates in Upper-Atmosphere Hypersonic Flows'. The goal of this project was to apply a recently proposed approach for the Direct Simulation Monte Carlo (DSMC) method to calculate chemical-reaction rates for high-temperature atmospheric species. The new DSMC model reproduces measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular properties, the new model is inherently able to predict reaction rates for arbitrary nonequilibrium conditions. DSMC non-equilibrium reaction rates are compared to Park's phenomenological non-equilibrium reaction-rate model, the predominant model for hypersonic-flow-field calculations. For near-equilibrium conditions, Park's model is in good agreement with the DSMC-calculated reaction rates. For far-from-equilibrium conditions, corresponding to a typical shock layer, the difference between the two models can exceed 10 orders of magnitude. The DSMC predictions are also found to be in very good agreement with measured and calculated non-equilibrium reaction rates. Extensions of the model to reactions typically found in combustion flows and ionizing reactions are also found to be in very good agreement with available measurements, offering strong evidence that this is a viable and reliable technique to predict chemical reaction rates.

  11. On the interaction of isotopic exchange processes with photochemical reactions in atmospheric oxides of nitrogen

    SciTech Connect

    Freyer, H.D.; Kley, D.; Volz-Thomas, A.; Kobel, K.

    1993-08-20

    The authors study the isotopic composition of nitic oxide and nitrogen dioxide in the atmosphere. They model the observed results for {sup 15}N/{sup 14}N ratios in terms of isotopic exchange reactions with ozone and photolytic reactions on the oxides. They find there has to be an interaction of these two reactions, in conjunction with seasonl variations of nitrogen oxide/ozone ratios, to account for observed isotopic ratios of the nitrogen isotopes.

  12. The Hydroxyl Radical Reaction Rate Constant and Products of Dimethyl Succinate

    DTIC Science & Technology

    2008-03-01

    AFRL-RX-TY-TR-2008-4522 THE HYDROXYL RADICAL REACTION RATE CONSTANT AND PRODUCTS OF DIMETHYL SUCCINATE Sheryl E. Calidonna and...the gas-phase hydroxyl radical reaction with dimethyl succinate. Additional reports and publications resulting from this work unit are not described...herein but are listed below for reference. Baxley, J.Steven and J.R. Wells, “The Hydroxyl Radical Rate Constant and Atmospheric Transforamtion

  13. Middle atmosphere heating by exothermic chemical reactions involving odd-hydrogen species

    NASA Technical Reports Server (NTRS)

    Mlynczak, Martin G.; Solomon, Susan

    1991-01-01

    The rate of heating which occurs in the middle atmosphere due to four exothermic reactions involving members of the odd-hydrogen family is calculated. The following reactions are considered: O + OH yields O2 + H; H + O2 + M yields HO2 + M; H + O3 yields OH + O2; and O + HO2 yields OH + O2. It is shown that the heating rates due to these reactions rival the oxygen-related heating rates conventionally considered in middle-atmosphere models. The conversion of chemical potential energy into molecular translational energy (heat) by these odd-hydrogen reactions is shown to be a significant energy source in the middle atmosphere that has not been previously considered.

  14. Middle atmosphere heating by exothermic chemical reactions involving odd-hydrogen species

    NASA Technical Reports Server (NTRS)

    Mlynczak, Martin G.; Solomon, Susan

    1991-01-01

    The rate of heating which occurs in the middle atmosphere due to four exothermic reactions involving members of the odd-hydrogen family is calculated. The following reactions are considered: O + OH yields O2 + H; H + O2 + M yields HO2 + M; H + O3 yields OH + O2; and O + HO2 yields OH + O2. It is shown that the heating rates due to these reactions rival the oxygen-related heating rates conventionally considered in middle-atmosphere models. The conversion of chemical potential energy into molecular translational energy (heat) by these odd-hydrogen reactions is shown to be a significant energy source in the middle atmosphere that has not been previously considered.

  15. THE OZONE REACTION WITH BUTADIENE: FORMATION OF TOXIC PRODUCTS. (R826236)

    EPA Science Inventory

    Abstract

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product ...

  16. THE OZONE REACTION WITH BUTADIENE: FORMATION OF TOXIC PRODUCTS. (R826236)

    EPA Science Inventory

    Abstract

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product ...

  17. Elusive anion growth in Titan's atmosphere: Low temperature kinetics of the C3N- + HC3N reaction

    NASA Astrophysics Data System (ADS)

    Bourgalais, Jérémy; Jamal-Eddine, Nour; Joalland, Baptiste; Capron, Michael; Balaganesh, Muthiah; Guillemin, Jean-Claude; Le Picard, Sébastien D.; Faure, Alexandre; Carles, Sophie; Biennier, Ludovic

    2016-06-01

    Ion chemistry appears to be deeply involved in the formation of heavy molecules in the upper atmosphere of Titan. These large species form the seeds of the organic aerosols responsible for the opaque haze surrounding the biggest satellite of Saturn. The chemical pathways involving individual anions remain however mostly unknown. The determination of the rates of the elementary reactions with ions and the identification of the products are essential to the progress in our understanding of Titan's upper atmosphere. We have taken steps in that direction through the investigation of the low temperature reactivity of C3N- , which was tentatively identified in the spectra measured by the CAPS-ELS instrument of the Cassini spacecraft during its high altitude flybys. The reaction of this anion with HC3N, one of the most abundant trace organics in the atmosphere, has been studied over the 49-294 K temperature range in uniform supersonic flows using the CRESU technique. The proton transfer is found to be the main exit channel (>91%) of the C315N- + HC3N reaction. It remains however indistinguishable with the non-isotopically labeled C314N- reactant. The T - 1 / 2 temperature dependence of this proton transfer reaction and its global rate are reasonably well reproduced theoretically using an average dipole orientation model. A minor exit channel, reactive detachment (< 9%), has also been uncovered, although the nature of the neutral products has not been determined. It is concluded that the C314N- + HC3N reaction cannot contribute to the growth of molecular anions in the upper atmosphere of Titan. Due to the low branching into the neutral exit channel, it cannot contribute either to the growth of neutrals even assuming a complete mass transfer.

  18. Energy distribution among reaction products. V.

    NASA Technical Reports Server (NTRS)

    Anlauf, K. G.; Horne, D. S.; Macdonald, R. G.; Polanyi, J. C.; Woodall, K. B.

    1972-01-01

    Discussion of three reactions, one point of theoretical interest being the predicted correlation between barrier height and barrier location. The H + Br 2 reaction having a lower activation barrier than H + Cl 2, should have an earlier barrier, and hence a greater percentage attractive energy release and higher efficiency of vibrational excitation. Information is developed concerning the effect of isotopic substitution in the pair of reactions H + Cl 2 and D + Cl 2. The 'arrested relaxation' method was used. Essentially, the method involves reacting two diffuse reagent beams in a reaction vessel with background pressure less than 0.001 torr, and with walls cooled by liquid nitrogen or liquid helium.

  19. Role of microorganisms in the consumption and production of atmospheric carbon monoxide by soil.

    PubMed

    Conrad, R; Seiler, W

    1980-09-01

    Consumption and production of atmospheric CO was measured under field conditions in three different types of soil. CO was consumed by an apparent first-order reaction and produced by an apparent zero-order reaction, resulting in a dynamic equilibrium with the consumption of atmospheric CO as the net reaction. CO consumption was higher in summer than in winter. Laboratory experiments on five different soil types showed that CO consumption was strongly inhibited by the presence of streptomycin or cycloheximide (Actidione), or both. Thus, eucaryotic as well as procaryotic microorganisms were apparently responsible for the observed CO consumption. The aerobic carboxydobacterium Pseudomonas carboxydovorans added to sterile soil was able to utilize the low amounts (ca. 0.7 ppmv) of CO present in laboratory air. CO was consumed by soil under aerobic as well as anaerobic conditions. Anaerobic preincubation of the soil stimulated the anaerobic CO consumption and reduced the aerobic CO consumption. In contrast to CO consumption, CO production was stimulated by autoclaving, by ultraviolet-irradiation, by fumigation with NH(3) or CHCl(3), by treatment with streptomycin or cycloheximide or both, by addition of NaCN, NaN(3), or Na(2)HAsO(4) (or all three) in the presence of glucose under an atmosphere of pure oxygen, or by a drying and rewetting procedure. The consumption of atmospheric CO by soil is a microbial process, but the production of CO is apparently not a metabolic process.

  20. Reactions of Azine Anions with Nitrogen and Oxygen Atoms: Implications for Titan's Upper Atmosphere and Interstellar Chemistry.

    PubMed

    Wang, Zhe-Chen; Cole, Callie A; Demarais, Nicholas J; Snow, Theodore P; Bierbaum, Veronica M

    2015-08-26

    Azines are important in many extraterrestrial environments, from the atmosphere of Titan to the interstellar medium. They have been implicated as possible carriers of the diffuse interstellar bands in astronomy, indicating their persistence in interstellar space. Most importantly, they constitute the basic building blocks of DNA and RNA, so their chemical reactivity in these environments has significant astrobiological implications. In addition, N and O atoms are widely observed in the ISM and in the ionospheres of planets and moons. However, the chemical reactions of molecular anions with abundant interstellar and atmospheric atomic species are largely unexplored. In this paper, gas-phase reactions of deprotonated anions of benzene, pyridine, pyridazine, pyrimidine, pyrazine, and s-triazine with N and O atoms are studied both experimentally and computationally. In all cases, the major reaction channel is associative electron detachment; these reactions are particularly important since they control the balance between negative ions and free electron densities. The reactions of the azine anions with N atoms exhibit larger rate constants than reactions of corresponding chain anions. The reactions of azine anions with O atoms are even more rapid, with complex product patterns for different reactants. The mechanisms are studied theoretically by employing density functional theory; spin conversion is found to be important in determining some product distributions. The rich gas-phase chemistry observed in this work provides a better understanding of ion-atom reactions and their contributions to ionospheric chemistry as well as the chemical processing that occurs in the boundary layers between diffuse and dense interstellar clouds.

  1. Plant surface reactions: an ozone defence mechanism impacting atmospheric chemistry

    NASA Astrophysics Data System (ADS)

    Jud, W.; Fischer, L.; Canaval, E.; Wohlfahrt, G.; Tissier, A.; Hansel, A.

    2015-07-01

    Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. Plant injuries have been linked to the uptake of ozone through stomatal pores and oxidative damage of the internal leaf tissue. But a striking question remains: how much ozone effectively enters the plant through open stomata and how much is lost by chemical reactions at the plant surface? In this laboratory study we could show that semi-volatile organic compounds exuded by the glandular trichomes of different Nicotiana tabacum varieties are an efficient ozone sink at the plant surface. In our experiments, different diterpenoid compounds were responsible for a strongly variety dependent ozone uptake of plants under dark conditions, when stomatal pores are almost closed. Surface reactions of ozone were accompanied by prompt release of oxygenated volatile organic compounds, which could be linked to the corresponding precursor compounds: ozonolysis of cis-abienol (C20H34O) - a diterpenoid with two exocyclic double bonds - caused emissions of formaldehyde (HCHO) and methyl vinyl ketone (C4H6O). The ring-structured cembratrien-diols (C20H34O2) with three endocyclic double bonds need at least two ozonolysis steps to form volatile carbonyls such as 4-oxopentanal (C5H8O2), which we could observe in the gas phase, too. Fluid dynamic calculations were used to model ozone distribution in the diffusion limited leaf boundary layer under daylight conditions. In the case of an ozone-reactive leaf surface, ozone gradients in the vicinity of stomatal pores are changed in such a way, that ozone flux through the open stomata is strongly reduced. Our results show that unsaturated semi-volatile compounds at the plant surface should be considered as a source of oxygenated volatile organic compounds, impacting gas phase chemistry, as well as efficient ozone sink improving the ozone tolerance of plants.

  2. Step Towards Modeling the Atmosphere of Titan: State-Selected Reactions of O+ with Methane

    NASA Astrophysics Data System (ADS)

    Hrušák, J.; Paidarová, I.

    2016-11-01

    Methane conversion and in particular the formation of the C-O bond is one of fundamental entries to organic chemistry and it appears to be essential for understanding parts of atmospheric chemistry of Titan, but, in broader terms it might be also relevant for Earth-like exoplanets. Theoretical study of the reactions of methane with atomic oxygen ion in its excited electronic states requires treating simultaneously at least 19 electronic states. Development of a computational strategy that would allow chemically reasonable and computationally feasible treatment of the CH4 (X)/O+ (2D, 2P) system is by far not trivial and it requires careful examination of all the complex features of the corresponding 19 potential energy surfaces. Before entering the discussion of the rich (photo) chemistry, inspection of the long range behavior of the system with focus on electric dipole transition moments is required. Our calculations show nonzero probability for the reactants to decay before entering the multiple avoided crossings region of the [CH4 + O → products]+ reaction. For the CH4/O+ (2P) system non-zero transition moment probabilities occur over the entire range of considered C-O distances (up to 15 Å), while for the CH4/O+ (2D) system these probabilities are lower by one order of magnitude and were found only at C-O distances smaller than 6 Å.

  3. Step Towards Modeling the Atmosphere of Titan: State-Selected Reactions of O(+) with Methane.

    PubMed

    Hrušák, J; Paidarová, I

    2016-11-01

    Methane conversion and in particular the formation of the C-O bond is one of fundamental entries to organic chemistry and it appears to be essential for understanding parts of atmospheric chemistry of Titan, but, in broader terms it might be also relevant for Earth-like exoplanets. Theoretical study of the reactions of methane with atomic oxygen ion in its excited electronic states requires treating simultaneously at least 19 electronic states. Development of a computational strategy that would allow chemically reasonable and computationally feasible treatment of the CH4 (X)/O(+) ((2)D, (2)P) system is by far not trivial and it requires careful examination of all the complex features of the corresponding 19 potential energy surfaces. Before entering the discussion of the rich (photo) chemistry, inspection of the long range behavior of the system with focus on electric dipole transition moments is required. Our calculations show nonzero probability for the reactants to decay before entering the multiple avoided crossings region of the [CH4 + O → products](+) reaction. For the CH4/O(+) ((2)P) system non-zero transition moment probabilities occur over the entire range of considered C-O distances (up to 15 Å), while for the CH4/O(+) ((2)D) system these probabilities are lower by one order of magnitude and were found only at C-O distances smaller than 6 Å.

  4. Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

    NASA Astrophysics Data System (ADS)

    Babikov, Dmitri

    2017-03-01

    A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: 33S, 34S, and 36S. Interestingly, the ratio of capital ΔΔ values obtained within this model for 33S and 36S is -1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth.

  5. Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth

    PubMed Central

    Babikov, Dmitri

    2017-01-01

    A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: 33S, 34S, and 36S. Interestingly, the ratio of capital Δ values obtained within this model for 33S and 36S is −1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth. PMID:28258172

  6. Recombination reactions as a possible mechanism of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth.

    PubMed

    Babikov, Dmitri

    2017-03-21

    A hierarchy of isotopically substituted recombination reactions is formulated for production of sulfur allotropes in the anoxic atmosphere of Archean Earth. The corresponding system of kinetics equations is solved analytically to obtain concise expressions for isotopic enrichments, with focus on mass-independent isotope effects due to symmetry, ignoring smaller mass-dependent effects. Proper inclusion of atom-exchange processes is shown to be important. This model predicts significant and equal depletions driven by reaction stoichiometry for all rare isotopes: (33)S, (34)S, and (36)S. Interestingly, the ratio of capital [Formula: see text] values obtained within this model for (33)S and (36)S is -1.16, very close to the mass-independent fractionation line of the Archean rock record. This model may finally offer a mechanistic explanation for the striking mass-independent fractionation of sulfur isotopes that took place in the Archean atmosphere of Earth.

  7. Mineralization of atmospheric CO2 via fluid reaction with mafic/ultramafic rocks

    NASA Astrophysics Data System (ADS)

    Westfield, I. T.; Kendall, T. A.; Ries, J. B.

    2011-12-01

    Atmospheric CO2 has increased nearly 50% since the Industrial Revolution, due primarily to increased fossil fuel combustion, cement production, and deforestation. Although subterranean reservoirs are presently considered the most viable sink for anthropogenically liberated CO2, concerns exist over the stability of these systems and their impacts on regional tectonics, aquifers, and subterranean microbial ecosystems. Direct mineralization of CO2 at the Earth's surface provides an alternative capable of generating useful carbon-negative mineral byproducts that may be used to supplement or replace conventional carbon-positive building materials, like cement. However, mineralization of anthropogenic CO2 requires large sources of alkalinity to convert CO2 to CO32-, and divalent cations (e.g., Mg2+, Ca2+, Fe2+, etc.) to bond with the aqueous CO32-. Ultramafic and mafic rocks, such as peridotites, serpentinites, and basalts, are globally abundant, naturally occurring sources of the divalent cations, and alkalinity required for CO2 mineralization. Here, we present the results of accelerated reactions between ultramafic/mafic rocks, water, and CO2/N2 gases, aimed at quantifying the carbonation potential of mafic/ultramafic rocks. Rock-fluid-gas batch reactions were carried out in vented 4 L borosilicate glass flasks filled with 3 L DI water and 200 g acetone-washed, 49-180μm-diameter grains of four ultramafic/mafic rock types: peridotite, dunite, websterite and basalt. Each of the four rock-water mixtures was reacted under pure CO2 and pure N2 and at 25 and 200 °C, for a total of 16 reactions. Mixtures were continuously heated and stirred for 14 days. Samples (330 mL) were obtained at 0, 1, 6, 24, 48, 96, 168, and 336 hrs and filtered at 0.4 μm. The pH of filtered samples was measured with a single-junction Ag/AgCl glass electrode, salinity was determined with a conductivity probe, total alkalinity (TA) was determined by closed-cell potentiometric Gran titration, and DIC

  8. Products of the reaction of chlorine atoms and ozone

    NASA Technical Reports Server (NTRS)

    Hall, J. H., Jr.; Merideth, C. W.; Bhatia, S.; Guillory, W. A.; Gayles, J. N.

    1976-01-01

    Preliminary matrix-isolation infrared spectroscopic studies of the gas-phase reaction of chlorine atoms and ozone are reported. It was shown that the major product of the reaction is the symmetric OClO radical, while very little of the asymmetric ClOO radical is produced. It was also shown that the presence of O2 enhances the OClO production and the ClOO is the primary product in the reaction of Cl atoms and pure O2. The radical ClO was observed for the first time in a gas-phase reaction of Cl and O3. A mechanism for these observations is proposed.

  9. Generation of mutagenic transformation products during the irradiation of simulated urban atmospheres

    SciTech Connect

    Kleindienst, T.E.; Smith, D.F.; Hudgens, E.E.; Claxton, L.D.; Bufalini, J.J.

    1992-01-01

    Mixtures of air pollutants simulating urban atmospheres were irradiated in a smog chamber, and the resultant products were monitored for the production of mutagenic and other hazardous compounds. The production of biologically active compounds was detected through use of the Ames mutagenicity assay with Salmonella typhimurium, strain TA100. Irradiations of the pollutant mixture were conducted at HC/NOx ratios of 20 and 11. Overall, the mutagenicity of the products and the formation of oxygenated primary and secondary reactions products were greater for the simulations with the higher initial HC/NOx value. The origin of the mutagenicity from the reactant mixture was examined by conducting experiments with individual paraffinic, olefinic, and aromatic hydrocarbons. The chemicals examined during this aspect of the study were the paraffin n-butane, the olefin propylene, and the aromatic toluene. For the conditions studied, the activity of the toluene products was generally greater than that of propylene or n-butane, and the propylene products showed greater activity than did the n-butane products. The production of n-butane products was generally limited by its low rate of reaction with hydroxyl radicals. Photooxidation products from secondary reactions were most important in the toluene and propylene systems.

  10. Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

    NASA Technical Reports Server (NTRS)

    Hynes, A. J.; Wine, P. H.

    1997-01-01

    The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic

  11. Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

    NASA Technical Reports Server (NTRS)

    Hynes, A. J.; Wine, P. H.

    1997-01-01

    The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic

  12. Reactions of isoprene and sulphoxy radical-anions - a possible source of atmospheric organosulphites and organosulphates

    NASA Astrophysics Data System (ADS)

    Rudziński, K. J.; Gmachowski, L.; Kuznietsova, I.

    2009-03-01

    Transformation of isoprene coupled with auto-oxidation of SIV in aqueous solutions was studied experimentally and by chemical-kinetic modelling over a broad range of solution acidities (pH=3-9) to complement the research on aqueous-phase and heterogeneous transformation of isoprene reported recently by many laboratories. Isoprene significantly slowed down the auto-oxidation in acidic and basic solutions, and accelerated it slightly in neutral solutions. Simultaneously, production of sulphate ions and formation of solution acidity were significantly reduced. Formation of sulphite and sulphate derivatives of isoprene - sulphurous acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=163), sulphurous acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=165), sulphuric acid mono-(2-methyl-4-oxo-but-2-enyl) ester (m/z=179), sulphuric acid mono-(4-hydroxy-2-methyl-but-2-enyl) ester (m/z=181), and possible structural isomers of these species - was indicated by electrospray ionisation mass spectrometric analysis of post-reaction mixtures. The experimental results were explained by changes in a subtle quantitative balance of three superimposed processes whose rates depended in different manner on the acidity of reacting solutions - the scavenging of sulphoxy radical-anions by isoprene, the formation of sulphoxy radical-anions during further reactions of isoprene radicals, and the auto-oxidation of SIV itself. A chemical mechanism based on this idea was explored numerically to show good agreement with experimental data. In basic and neutral solutions, the model overestimated the consumption of isoprene, probably because reactions of primary sulphite and sulphate derivatives of isoprene with sulphoxy radical-anions were not included. Interaction of isoprene with sulphur(IV) species and oxygen can possibly result in formation of new organosulphate and organosulphite components of atmospheric aerosols and waters, and influence the distribution of reactive sulphur and oxygen species

  13. Non-thermal production and escape of OH from the upper atmosphere of Mars

    NASA Astrophysics Data System (ADS)

    Gacesa, M.; Lewkow, N.; Kharchenko, V.

    2017-03-01

    We present a theoretical analysis of formation and kinetics of hot OH molecules in the upper atmosphere of Mars produced in reactions of thermal molecular hydrogen and energetic oxygen atoms. Two major sources of energetic O considered are the photochemical production, via dissociative recombination of O2+ ions, and energizing collisions with fast atoms produced by the precipitating Solar Wind (SW) ions, mostly H+ and He2+ , and energetic neutral atoms (ENAs) originating in the charge-exchange collisions between the SW ions and atmospheric gases. Energizing collisions of O with atmospheric secondary hot atoms, induced by precipitating SW ions and ENAs, are also included in our consideration. The non-thermal reaction O + H2(v, j) → H + OH(v‧, j‧) is described using recent quantum-mechanical state-to-state cross sections, which allow us to predict non-equilibrium distributions of excited rotational and vibrational states (v‧, j‧) of OH and expected emission spectra. A fraction of produced translationally hot OH is sufficiently energetic to overcome Mars' gravitational potential and escape into space, contributing to the hot corona. We estimate its total escape flux from the dayside of Mars for low solar activity conditions at about 1.1 × 1023 s-1 , or about 0.1% of the total escape rate of atomic O and H. The described non-thermal OH production mechanism is general and expected to contribute to the evolution of atmospheres of the planets, satellites, and exoplanets with similar atmospheric compositions.

  14. Atmospheric chemistry of sulfuryl fluoride: reaction with OH radicals, Cl atoms and O3, atmospheric lifetime, IR spectrum, and global warming potential.

    PubMed

    Andersen, M P Sulbaek; Blake, D R; Rowland, F S; Hurley, M D; Wallington, T J

    2009-02-15

    Sulfuryl fluoride (SO2F2) is a radiatively active industrial chemical released into the atmosphere in significant (ktonne/ year) quantities. The potential for SO2F2 to contribute to radiative forcing of climate change needs to be assessed. Long path length FTIR/smog chamber techniques were used to investigate the kinetics of the gas-phase reactions of Cl atoms, OH radicals, and O3 with SO2F2, in 700 Torr total pressure of air or N2 at 296 +/- 1 K. Upper limits of k(Cl + SO2F2) < 9 x 10(-19), k(OH + SO2F2) < 1.7 x 10(-14) and k(O3 + SO2F2) < 5.5 x 10(-24) cm3 molecule(-1) s(-1) were determined. Reaction with Cl atoms, OH radicals, or O3 does not provide an efficient removal mechanism for SO2F2. The infrared spectrum of SO2F2 is reported and a radiative efficiency of 0.196 W m(-2) ppbv(-1) was calculated. Historic production data estimates are presented which provide an upper limit for expected atmospheric concentrations. The radiative forcing of climate change associated with emissions of SO2F2 depends critically on the atmospheric lifetime of SO2F2. Further research is urgently needed to define the magnitude of potential nonatmospheric sinks.

  15. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    DOE PAGES

    Osborn, David L.

    2017-03-15

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low temperature combustion and the oxidation of volatile organic compounds in earth’s atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization make characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, while master equation methods enable a holistic treatment of both sequential andmore » well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.« less

  16. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

    NASA Astrophysics Data System (ADS)

    Osborn, David L.

    2017-05-01

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

  17. Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications

    PubMed Central

    Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto; Kerminen, Veli-Matti; Junninen, Heikki; Stratmann, Frank; Herrmann, Hartmut; Guenther, Alex B.; Worsnop, Douglas R.; Kulmala, Markku; Ehn, Mikael; Sipilä, Mikko

    2015-01-01

    Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget. PMID:26015574

  18. Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications.

    PubMed

    Jokinen, Tuija; Berndt, Torsten; Makkonen, Risto; Kerminen, Veli-Matti; Junninen, Heikki; Paasonen, Pauli; Stratmann, Frank; Herrmann, Hartmut; Guenther, Alex B; Worsnop, Douglas R; Kulmala, Markku; Ehn, Mikael; Sipilä, Mikko

    2015-06-09

    Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget.

  19. The Influence of CO2 Admixtures on the Product Composition in a Nitrogen-Methane Atmospheric Glow Discharge Used as a Prebiotic Atmosphere Mimic.

    PubMed

    Mazankova, V; Torokova, L; Krcma, F; Mason, N J; Matejcik, S

    2016-11-01

    This work extends our previous experimental studies of the chemistry of Titan's atmosphere by atmospheric glow discharge. The Titan's atmosphere seems to be similarly to early Earth atmospheric composition. The exploration of Titan atmosphere was initiated by the exciting results of the Cassini-Huygens mission and obtained results increased the interest about prebiotic atmospheres. Present work is devoted to the role of CO2 in the prebiotic atmosphere chemistry. Most of the laboratory studies of such atmosphere were focused on the chemistry of N2 + CH4 mixtures. The present work is devoted to the study of the oxygenated volatile species in prebiotic atmosphere, specifically CO2 reactivity. CO2 was introduced to the standard N2 + CH4 mixture at different mixing ratio up to 5 % CH4 and 3 % CO2. The reaction products were characterized by FTIR spectroscopy. This work shows that CO2 modifies the composition of the gas phase with the detection of oxygenated compounds: CO and others oxides. There is a strong influence of CO2 on increasing concentration other products as cyanide (HCN) and ammonia (NH3).

  20. The Influence of CO2 Admixtures on the Product Composition in a Nitrogen-Methane Atmospheric Glow Discharge Used as a Prebiotic Atmosphere Mimic

    NASA Astrophysics Data System (ADS)

    Mazankova, V.; Torokova, L.; Krcma, F.; Mason, N. J.; Matejcik, S.

    2016-11-01

    This work extends our previous experimental studies of the chemistry of Titan's atmosphere by atmospheric glow discharge. The Titan's atmosphere seems to be similarly to early Earth atmospheric composition. The exploration of Titan atmosphere was initiated by the exciting results of the Cassini-Huygens mission and obtained results increased the interest about prebiotic atmospheres. Present work is devoted to the role of CO2 in the prebiotic atmosphere chemistry. Most of the laboratory studies of such atmosphere were focused on the chemistry of N2 + CH4 mixtures. The present work is devoted to the study of the oxygenated volatile species in prebiotic atmosphere, specifically CO2 reactivity. CO2 was introduced to the standard N2 + CH4 mixture at different mixing ratio up to 5 % CH4 and 3 % CO2. The reaction products were characterized by FTIR spectroscopy. This work shows that CO2 modifies the composition of the gas phase with the detection of oxygenated compounds: CO and others oxides. There is a strong influence of CO2 on increasing concentration other products as cyanide (HCN) and ammonia (NH3).

  1. Kinetic and photochemical data for atmospheric chemistry reactions of the nitrogen oxides

    NASA Technical Reports Server (NTRS)

    Hampson, R. F., Jr.

    1980-01-01

    Data sheets for thermal and photochemical reactions of importance in the atmospheric chemistry of the nitrogen oxides are presented. For each reaction the available experimental data are summarized and critically evaluated, and a preferred value of the rate coefficient is given. The selection of the preferred value is discussed and an estimate of its accuracy is given. For the photochemical process, the data are summarized, and preferred for the photoabsorption cross section and primary quantum yields are given.

  2. Comparison of the Reaction Behavior of Hexagonal Silicon Carbide Powder in Different Atmospheres

    NASA Astrophysics Data System (ADS)

    Wang, Enhui; Hou, Xinmei; Chen, Junhong; Chou, Kuo-Chih

    2017-07-01

    The reaction behavior of hexagonal silicon carbide (h-SiC) powder under different atmospheres including dry air, air containing 20 vol pct water vapor, and Ar containing 20 vol pct water vapor at 1373 K to 1773 K (1100 °C to 1500 °C) for 10 hours has been investigated and compared. The SiC powder exhibits good oxidation resistance up to 1373 K (1100 °C) and its reaction behavior depends on both the temperature and atmosphere. Below 1773 K (1500 °C), water vapor can promote the formation of pores and enhance the oxidation of SiC powder. However, it tends to aggravate the surface sintering and intensify the volatilization reaction at 1773 K (1500 °C). This phenomenon is further verified with the increasing water vapor content. Based on this, a gas-solid model is adopted to deal with the corresponding reaction kinetics, and especially both oxidation and volatilization reactions are considered when dealing with the reaction kinetics of SiC powder in water-containing atmospheres.

  3. Comparison of the Reaction Behavior of Hexagonal Silicon Carbide Powder in Different Atmospheres

    NASA Astrophysics Data System (ADS)

    Wang, Enhui; Hou, Xinmei; Chen, Junhong; Chou, Kuo-Chih

    2017-10-01

    The reaction behavior of hexagonal silicon carbide (h-SiC) powder under different atmospheres including dry air, air containing 20 vol pct water vapor, and Ar containing 20 vol pct water vapor at 1373 K to 1773 K (1100 °C to 1500 °C) for 10 hours has been investigated and compared. The SiC powder exhibits good oxidation resistance up to 1373 K (1100 °C) and its reaction behavior depends on both the temperature and atmosphere. Below 1773 K (1500 °C), water vapor can promote the formation of pores and enhance the oxidation of SiC powder. However, it tends to aggravate the surface sintering and intensify the volatilization reaction at 1773 K (1500 °C). This phenomenon is further verified with the increasing water vapor content. Based on this, a gas-solid model is adopted to deal with the corresponding reaction kinetics, and especially both oxidation and volatilization reactions are considered when dealing with the reaction kinetics of SiC powder in water-containing atmospheres.

  4. Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

    2011-12-01

    Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

  5. Mercury emission to atmosphere from primary Zn production in China.

    PubMed

    Li, Guanghui; Feng, Xinbin; Li, Zhonggen; Qiu, Guangle; Shang, Lihai; Liang, Peng; Wang, Dingyong; Yang, Yongkui

    2010-09-15

    Emissions of mercury (Hg) to air have regional and global impacts through long range transport in the atmosphere. Primary Zn production is regarded as an important anthropogenic Hg source in China, but research on its Hg emission is limited. To gain a better understanding of Hg emissions from Zn production activities in China, field investigations at four industrial-scale Zn production plants using electrostatic process with Hg removal (HP-WR), electrostatic process without Hg removal (HP-WOR), retort Zn production (RZ), imperial smelting process (ISP), and one artisanal Zn smelting process (AZ) were carried out. In the investigation, Hg emission factors are defined as how much Hg was emitted to the atmosphere per ton Zn produced during various Zn production methods and were estimated by using mass balance method. The results showed that the estimated Hg emission factors of Zn production were 5.7+/-4.0 g Hg t(-1) Zn for HP-WR, 31+/-22 g Hg t(-1) Zn for HP-WOR, 34+/-71 g Hg t(-1) Zn for RZ, 122+/-122 g Hg t(-1) Zn g t(-1) for ISP, and 75+/-115 g Hg t(-1) Zn for AZ. Approximately 80.7-104.2 t year(-1) of Hg was emitted to atmosphere from primary Zn production during the period of 2002-2006 in China. Copyright 2010 Elsevier B.V. All rights reserved.

  6. Gas-phase and particulate products from the atmospheric degradation of an isoxazole fungicide.

    PubMed

    Tortajada-Genaro, Luis Antonio; Borrás, Esther; Muñoz, Amalia

    2013-08-01

    The isoxazole structure is present in several pesticides. However, there is a lack of information about its degradation products after the release to the atmosphere. The main atmospheric reactions of hymexazol (5-methylisoxazol-3-ol), selected as representative model, were investigated at a large outdoor simulation chamber. The predominant products of atmospheric degradations were gaseous nitrogen derivates (nitric acid, nitrogen dioxide, nitrogen oxide, nitrous acid, and peroxyacetylnitrate), ozone, and small oxygenated compounds (formic acid, formaldehyde, and methylglyoxal). The aerosol yields were lower than 5%, and an OH rate-dependence was observed in the nucleation, particle growth, and size distribution. Also, the chemical composition of minor multi-oxygenated products was studied for OH-photo-oxidations. More than 20 products were detected in the gas or particulate phase. The most abundant were heterocyclic cleavage products with C4-chain and oxygenated moieties at positions 1 and 3, such as 3,4-dioxobutanoic acid, 3-oxobutanoic acid, and 3-oxobutanal. The suggested reaction pathway is the opening of heterocycle ring by the cleavage of N-O bond and C-N bond, releasing nitrogen oxides.

  7. Low-temperature Kinetic Studies of OH Radical Reactions Relevant to Planetary Atmospheres

    NASA Astrophysics Data System (ADS)

    Townsend, T. M.; Antiñolo, M.; Ballesteros, B.; Jimenez, E.; Canosa, A.

    2011-05-01

    In the solar system, the temperature (T) of the atmosphere of giant planets or their satellites is only several tens of Kelvin (K). The temperature of the tropopause of Titan (satellite of Saturn) and the surface of Mars is 70 K and 210 K, respectively. In the Earth's atmosphere, T decreases from 298 K (surface) to 210 K close to the T-inversion region (tropopause). The principal oxidants in the Earth's lower atmosphere are ozone, the hydroxyl (OH) radical and hydrogen peroxide. A number of critical atmospheric chemical problems depend on the Earth's oxidising capacity, which is essentially the global burden of these oxidants. In the interstellar clouds and circumstellar envelopes, OH radicals have also been detected. As the chemistry of atmospheres is highly influenced by temperature, the knowledge of the T-dependence of the rate coefficients for OH-reactions (k) is the key to understanding the underlying molecular mechanisms. In general, these reactions take place on a short temporal scale. Therefore, a detection technique with high temporal resolution is required. Measurements of k at low temperatures can be achieved by maintaining a thermalised environment using either cryogenic cooling (T>200 K) or supersonic gas expansion with a Laval nozzle (several tens of K). The pulsed laser photolysis technique coupled with laser induced fluorescence detection has been widely used in our laboratory to determine the rate coefficients of OH-reactions with different volatile organic compounds, such as alcohols (1), saturated and unsaturated aliphatic aldehydes (2), linear ketones (3), as a function of temperature (260 350 K). An experimental system based on the CRESU (Cinetique de Reaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique is currently under construction. This technique will allow the performance of kinetic studies of OH-reactions of astrophysical interest at temperatures lower than 200 K.

  8. Production of radioactive nuclides in inverse reaction kinematics

    NASA Astrophysics Data System (ADS)

    Traykov, E.; Rogachevskiy, A.; Bosswell, M.; Dammalapati, U.; Dendooven, P.; Dermois, O. C.; Jungmann, K.; Onderwater, C. J. G.; Sohani, M.; Willmann, L.; Wilschut, H. W.; Young, A. R.

    2007-03-01

    Efficient production of short-lived radioactive isotopes in inverse reaction kinematics is an important technique for various applications. It is particularly relevant when the isotope of interest is only a few nucleons away from a stable isotope. In this article production via charge exchange and stripping reactions in combination with a magnetic separator is explored. The relation between the separator transmission efficiency, the production yield, and the choice of beam energy is discussed. The results of some exploratory experiments will be presented.

  9. Comment on 'Propellant production from the Martian atmosphere'

    NASA Technical Reports Server (NTRS)

    Ruppe, H. O.

    1993-01-01

    The optimism of the Tauber et al. (1992) note on photosynthetic production of spacecraft fuels from Martian atmospheric gases is presently noted, in conjunction with the need for prior missions' verification of such a system. Two of the original authors reply that their solar cell array assumptions are conservative in light of plausible performance projections for 2010-decade technology.

  10. Heterogeneous production of cloud condensation nuclei in the marine atmosphere

    SciTech Connect

    Hegg, D.A. )

    1990-11-01

    Model calculations are presented which indicate that newly created particles in the marine atmosphere will commonly only be able to achieve sizes, by means of gas-phase processes, sufficient to activate a cumuliform clouds. Aqueous sulfate production in such clouds will be generally necessary to grow them large enough to activate in marine stratus clouds.

  11. An investigation of oxidation products and SOA yields from OH + pesticide reactions

    NASA Astrophysics Data System (ADS)

    Murschell, T.; Friedman, B.; Link, M.; Farmer, D.

    2016-12-01

    Pesticides are used globally in agricultural and residential areas. After application and/or volatilization from a surface, these compounds can be transported over long distances in the atmosphere. However, their chemical fate, including oxidation and gas-particle partitioning in the atmosphere, is not well understood. We present gas and particle measurements of oxidation products from pesticide + OH reactions using a dynamic solution injection system coupled to an Oxidative Flow Reactor. Products were detected with a High Resolution Time of Flight Iodide Chemical Mass Spectrometer (HR-ToF-CIMS) and a Size Mobility Particle Scanner (SMPS). The OFR allows pesticides to react with variable OH radical exposures, ranging from the equivalent of one day to a full week of atmospheric oxidative aging. In this work, we explore pesticide oxidation products from reaction with OH and ozone, and compare those products to photolysis reactions. Pesticides of similar chemical structures were explored, including acetochlor / metolachlor and permethrin / cypermethrin, to explore mechanistic differences. We present chemical parameters including average product oxidation state, average oxygen to carbon ratio, and potential secondary organic aerosol formation for each of these compounds.

  12. Meson Production in p+d Reactions

    NASA Astrophysics Data System (ADS)

    Klimala, W.; Betigeri, M.; Bojowald, J.; Budzanowski, A.; Chatterjee, A.; Ernst, J.; Freindl, L.; Frekers, D.; Garske, W.; Grewer, K.; Hamacher, A.; Ilieva, J.; Jarczyk, L.; Kilian, K.; Kliczewski, S.; Kolev, D.; Kutsarova, T.; Lieb, J.; Machner, H.; Magiera, A.; Nann, H.; Pentchev, L.; Plendl, H. S.; Protic, D.; Razen, B.; von Rossen, P.; Roy, B.; Siudak, R.; Smyrski, J.; Strzalkowski, A.; Tsenov, R.; Zwoll, K.

    2000-10-01

    Differential cross sections of the pd→ 3H π +/ 3He π 0 reactions were measured simultaneously at three beam momenta: 750 MeV/c, 800 MeV/c and 850 MeV/c. The differential cross section of the pd→ 3He η was measured at 1675 MeV/c beam momentum. All measurements cover a wide angular range in the CM system. The experiments were performed at the COSY accelerator in Juelich, Germany, by means of high purity Germanium Wall detector together with the magnetic spectrometer BIG KARL. Estimated cross sections were compared with the predictions of simple theoretical models. In case of isospin symmetric pd→ 3H π +/ 3He π 0 reactions, the average cross section ratio was estimated.

  13. Massive production of nanoparticles via mist reaction

    NASA Astrophysics Data System (ADS)

    Liu, Ran; Liu, Lei; Liu, Jing

    2009-06-01

    A novel conceptual nanoparticle fabrication method is proposed in this paper. It can be easily implemented for the preparation of micro or nanoparticles through a reaction between mists with different specific chemical compounds produced by ultrasonic atomization technology. Ultrasonic atomization is an established technology that easily atomizes liquid to produce very small droplets-in the orders of tens to hundreds of micrometers. The results reveal that metal oxide nanoparticles, such as iron oxide can be massively produced via reactions between metal chlorides and sodium carbonate in an experimental set-up based on physical and chemical principles. The density of the nanoparticle distribution is also investigated and determined to be dependent on the amount of mist reacted and the collection time. Moreover, since the vibrational frequency of ultrasound can be adjusted, we can control the size of micro-droplets of reactants, hence producing particles of different dimensions. Given that the double mist reaction method is easily controllable, environmentally friendly and extremely low in cost, it can potentially become a significant method for making micro/nano particles in the newly emerging field of nanofabrication and integration.

  14. Mutagenicity in Salmonella of a Simulated Urban-Smog Atmosphere Generated Using a Mobile Reaction Chamber

    EPA Science Inventory

    The EPA Mobile Reaction Chamber (MRC) is a 24-foot trailer containing a 14.3-m3 Teflon lined photochemical chamber used to generate simulated urban atmospheres. Photochemistry in the MRC is catalyzed by 120 fluorescent bulbs evenly mixed with black light bulbs and UV bulbs (300 &...

  15. Termolecular Ion-Molecules Reactions in Titan's Atmosphere. I. Principal Ions with Principal Neutrals

    NASA Technical Reports Server (NTRS)

    Anicich, V.; Milligan, D.; Fairley, D.; McEwan, M.

    1999-01-01

    The FA-SIFT experiment at Canterbury was used to determine some of the principal termolecular ion-molecule reactions that occur in Saturn's satellite Titan's atmosphere. The experiments were performed using both a pure nitrogen bath gas and a pure helium bath gas.

  16. Termolecular Ion-Molecules Reactions in Titan's Atmosphere. I. Principal Ions with Principal Neutrals

    NASA Technical Reports Server (NTRS)

    Anicich, V.; Milligan, D.; Fairley, D.; McEwan, M.

    1999-01-01

    The FA-SIFT experiment at Canterbury was used to determine some of the principal termolecular ion-molecule reactions that occur in Saturn's satellite Titan's atmosphere. The experiments were performed using both a pure nitrogen bath gas and a pure helium bath gas.

  17. Mutagenicity in Salmonella of a Simulated Urban-Smog Atmosphere Generated Using a Mobile Reaction Chamber

    EPA Science Inventory

    The EPA Mobile Reaction Chamber (MRC) is a 24-foot trailer containing a 14.3-m3 Teflon lined photochemical chamber used to generate simulated urban atmospheres. Photochemistry in the MRC is catalyzed by 120 fluorescent bulbs evenly mixed with black light bulbs and UV bulbs (300 &...

  18. Analysis of the effects of zonal averaging on reaction rate calculations in two-dimensional atmospheric models

    NASA Technical Reports Server (NTRS)

    Kaye, Jack A.

    1987-01-01

    The usual assumption by which chemical reaction rates are calculated in two-dimensional atmospheric models is by using a product of zonal means of rate coefficients and constituent concentrations rather than the rigorous zonal mean of the corresponding products. This assumption has been tested for the reactions O + NO2 yields NO + O2 and NO + O3 yields NO2 + O2 using mapped limb infrared monitor of the stratosphere data from the Nimbus 7 satellite and found to be quite satisfactory for winter 1979 at 60 deg N in the upper stratosphere. Relative differences between the two-dimensional averaged rate and the more rigorous rate, calculated from the full, longitudinally varying temperatures and mixing ratios, were small (usually below 5 percent) and exceeded 15 percent only during times of strong dynamical activity. At those times or locations where stratospheric circulation is primarily zonal, the two averages agreed to within a few percent.

  19. Quantum Chemical Studies of Reactions Involving Sulfur and Sulfur-Chlorine Compounds for Venus Atmospheric Modeling Networks

    NASA Astrophysics Data System (ADS)

    Woon, D. E.; Maffucci, D. M.; Herbst, E.

    2017-05-01

    We are characterizing reactions involving sulfur and sulfur-chlorine compounds thought to be relevant to Venus using high level quantum chemical theory and reaction rate theory in order to improve atmospheric modeling studies.

  20. Atmospheric Lifetimes of Very Short Lived Substances: OH Reaction Rate Constants of Stereoisomers and Pressure Dependent Reactions.

    NASA Astrophysics Data System (ADS)

    Orkin, Vladimir; Khamaganov, Victor; Kurylo, Michael

    2017-04-01

    The accuracy of OH kinetic data is of primary importance for the comprehensive modeling of any compound's atmospheric behavior and of its environmental impacts, such as its atmospheric residence time and its potential roles in stratospheric ozone depletion, global warming, and local pollution. Rate constants of OH reactions with hydrocarbons and halogenated hydrocarbons can now be determined with an accuracy of 2-3% over the temperature range 220 K to 370 K. This has been demonstrated in studies of OH reactions with various halogenated and non-substituted organics including alkanes, alkenes, alcohols, and ethers. Lower data scattering and higher measurement accuracy allow for rigorous statistical analysis of the results and can reveal often-missing details about the reactivity, such as the weak dependencies of the rate constant on the temperature, pressure dependences, and the effect of molecular geometry on the reactivity. This presentation will provide examples of several of these measurement results that were recently obtained in our laboratory. The estimated atmospheric lifetimes and global warming potentials will be reported.

  1. Reactions between Criegee Intermediates and the Inorganic Acids HCl and HNO3 : Kinetics and Atmospheric Implications.

    PubMed

    Foreman, Elizabeth S; Kapnas, Kara M; Murray, Craig

    2016-08-22

    Criegee intermediates (CIs) are a class of reactive radicals that are thought to play a key role in atmospheric chemistry through reactions with trace species that can lead to aerosol particle formation. Recent work has suggested that water vapor is likely to be the dominant sink for some CIs, although reactions with trace species that are sufficiently rapid can be locally competitive. Herein, we use broadband transient absorption spectroscopy to measure rate constants for the reactions of the simplest CI, CH2 OO, with two inorganic acids, HCl and HNO3 , both of which are present in polluted urban atmospheres. Both reactions are fast; at 295 K, the reactions of CH2 OO with HCl and HNO3 have rate constants of 4.6×10(-11)  cm(3)  s(-1) and 5.4×10(-10)  cm(3)  s(-1) , respectively. Complementary quantum-chemical calculations show that these reactions form substituted hydroperoxides with no energy barrier. The results suggest that reactions of CIs with HNO3 in particular are likely to be competitive with those with water vapor in polluted urban areas under conditions of modest relative humidity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Low Temperature Studies of the Removal Reactions of 1CH2 with Relevance to the Atmosphere of Titan

    NASA Astrophysics Data System (ADS)

    Douglas, Kevin; Slater, Eloise; Feng, Wuhu; Blitz, Mark; Plane, John; Heard, Dwayne; Seakins, Paul

    2017-04-01

    The photolysis of methane by UV photons is the primary source of hydrocarbon radicals in the atmosphere of Titan and the giant planets. Although there is still significant uncertainty in the branching ratios of products, the production of the first singlet excited state of methylene, 1CH2, is thought to be a significant channel. Reactions of 1CH2 with methane (R1a) and hydrogen (R2a) are a significant source of methyl radicals, the recombination of which is the primary route to ethane on Titan (R3). The reaction of 1CH2 with acetylene is also a source of propargyl, C3H3, the recombination of which is the primary route to benzene on Titan. However, in addition to these reactions of 1CH2 leading to chemical products, there is also competition between inelastic electronic relaxation to form ground triplet state methylene, 3CH2 (R1b and R2b). Triplet methylene is much less reactive, and cannot undergo the complex insertion elimination reactions of singlet methylene. The main reaction of 3CH2 occurs with other radical species such as H (R4). 1CH2 + CH4 → CH3 + H2 (R1a) 1CH2 + CH4 → 3CH2 + CH4 (R1b) 1CH2 + H2 → CH3 + H (R2a) 1CH2 + H2 → 3CH2 + H2 (R2a) CH3 + CH3 (+M) → C2H6 (R3) 3CH2 + H → CH + H2 (R4) Using pulsed laser photolysis laser-induced fluorescence, we have studied the reaction kinetics for the removal of 1CH2 with N2, H2, CH4, C2H6, C2H4, C2H6, and O2 as a function of temperature. Low temperatures between 43 and 135 K were obtained using a pulsed Laval nozzle apparatus, while data at 160 K was obtained using a low flow reaction cell with cryogenic cooling. In addition to measuring total removal rates, the fraction of 1CH2 removed via electronic relaxation versus chemical reaction to products has also been investigated for H2 and CH4 at 160 and 73 K. Results show that that removal of 1CH2 by electronic relaxation increases with decreasing temperature. These experimental results indicate that the majority of 1CH2 formed in Titan's atmosphere will be

  3. Reactivity of CHI3 with OH radicals: X-abstraction reaction pathways (X = H, I), atmospheric chemistry, and nuclear safety.

    PubMed

    Sudolská, Mária; Louis, Florent; Cernušák, Ivan

    2014-10-09

    The X-abstraction (X = H, I) pathways in the reaction of CHI3 with OH radical, a possible iodoform removal process relevant to the Earth's atmosphere and conditions prevailing in the case of a nuclear accident, have been studied applying highly correlated ab initio quantum chemistry methods and canonical transition-state theory to obtain reaction energy profiles and rate constants. Geometry optimizations of reactants, products, molecular complexes, and transition states determined at the MP2/cc-pVTZ level of theory have been followed by DK-CCSD(T)/ANO-RCC single-point energy calculations. Further improvement of electronic energies has been achieved by applying spin-orbit coupling, corrections toward full configuration interaction, vibration contributions, and tunneling corrections. Calculated reaction enthalpies at 0 K are -108.2 and -5.1 kJ mol(-1) for the H- and I-abstraction pathways, respectively; the strongly exothermic H-abstraction pathway is energetically favored over the modestly exothermic I-abstraction one. The overall rate constant at 298 K based on our ab initio calculations is 4.90 × 10(-11) cm(3) molecule(-1) s(-1), with the I-abstraction pathway being the major channel over the temperature range of 250-2000 K. The CHI3 atmospheric lifetime with respect to the removal reaction with OH radical is predicted to be about 6 h, very short compared to that of other halomethanes.

  4. Isoprene reaction product concentrations in central Texas

    SciTech Connect

    Friedfeld, S.J.; Fraser, M.P.

    1999-07-01

    Biogenic hydrocarbons play an important role in the formation of tropospheric ozone. Studies have shown that Texas contains significant amounts of vegetation types that emit isoprene. In this study the atmospheric concentrations of methacrolein, formaldehyde, and other carbonyls were measured using the 2,4-dinitrophenyl hydrazine (DNPH) derivatization method on C18 cartridges and analyzed using high performance liquid chromatography (HPLC) with UV detection. Isoprene samples were collected concurrently by another group using stainless steel canisters and analyzed with GC-FID. The measurements were taken at one urban and three rural sites in Central Texas over a two-week period in August 1998. This paper reports the carbonyl concentrations observed, compares the concentrations with other studies, and discusses the temporal and spatial variability of the results.

  5. NO3 radical production from the reaction between the Criegee intermediate CH2OO and NO2.

    PubMed

    Ouyang, Bin; McLeod, Matthew W; Jones, Roderic L; Bloss, William J

    2013-10-28

    Formation of the NO3 radical was observed following photolysis of the CH2I2 + O2 system at 248 nm under ambient atmospheric boundary layer conditions (~760 Torr and 297 K) in the presence of NO2. The Criegee intermediate (CI) CH2OO is believed to be responsible for the NO3 production. The potential of such reactions to enhance the rate of NO3 production in the atmosphere is discussed.

  6. Modeling of chemical reactions between polyatomic molecules for atmospheric entry simulations with direct simulation Monte Carlo

    NASA Astrophysics Data System (ADS)

    Nizenkov, P.; Pfeiffer, M.; Mirza, A.; Fasoulas, S.

    2017-07-01

    For the simulation of atmospheric entry maneuvers at Mars and Saturn's Titan, the chemistry modeling of polyatomic molecules is implemented in the direct simulation Monte Carlo method within the reactive plasma flow solver PICLas. An additional reaction condition as well as the consideration of the vibrational degrees of freedom is described in the context of the total collision energy model. The treatment of reverse exchange and recombination reactions is discussed, where the low temperature exponent of the Arrhenius fit for methane dissociation limited the calculation of the reaction probability at relevant temperatures. An alternative method based on the equilibrium constant is devised. The post-reaction energy redistribution is performed under the assumption of equipartition of the remaining collisional energy. The implementation is verified for several reaction paths with simple reservoir simulations. Finally, the feasibility of the new chemistry model is demonstrated by a simulation of a trajectory point of Huygens probe at Titan.

  7. Fundamental Heterogeneous Reaction Chemistry Related to Secondary Organic Aerosols (SOA) in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Akimoto, H.

    2016-11-01

    Typical reaction pathways of formation of dicarboxylic acids, larger multifunctional compounds, oligomers, and organosulfur and organonitrogen compounds in secondary organic aerosols (SOA), revealed by laboratory experimental studies are reviewed with a short introduction to field observations. In most of the reactions forming these compounds, glyoxal, methyl glyoxal and related difunctional carbonyl compounds play an important role as precursors, and so their formation pathways in the gas phase are discussed first. A substantial discussion is then presented for the OH-initiated aqueous phase radical oxidation reactions of glyoxal and other carbonyls which form dicarboxylic acids, larger multifunctional compounds and oligomers, and aqueous-phase non-radical reactions which form oligomers, organosulfates and organonitrogen compounds. Finally, the heterogeneous oxidation reaction of gaseous O3, OH and NO3 with liquid and solid organic aerosols at the air-particle interface is discussed relating to the aging of SOA in the atmosphere.

  8. Field and laboratory studies of reactions between atmospheric water soluble organic acids and inorganic particles

    NASA Astrophysics Data System (ADS)

    Wang, Bingbing; Kelly, Stephen T.; Sellon, Rachel; Shilling, John; Tivanski, Alexei V.; Moffet, Ryan C.; Gilles, Mary K.; Laskin, Alexander

    2013-05-01

    Atmospheric inorganic particles undergo complex heterogeneous reactions that change their physicochemical properties. Depletion of chloride in sea salt particles was reported in previous field studies and was attributed to the acid displacement of chlorides with inorganic acids, such as nitric and sulfuric acids [1-2]. Recently, we showed that NaCl can react with water soluble organic acids (WSOA) and release gaseous hydrochloric acid (HCl) resulting in formation of organic salts [3]. A similar mechanism is also applicable to mixed WSOA/nitrate particles where multi-phase reactions are driven by the volatility of nitric acid. Furthermore, secondary organic material, which is a complex mixture of carboxylic acids, exhibits the same reactivity towards chlorides and nitrates. Here, we present a systematic study of reactions between atmospheric relevant WSOA, SOM, and inorganic salts including NaCl, NaNO3, and Ca(NO3)2 using complementary micro-spectroscopy analysis.

  9. Atmospheric chemistry. Direct kinetic measurement of the reaction of the simplest Criegee intermediate with water vapor.

    PubMed

    Chao, Wen; Hsieh, Jun-Ting; Chang, Chun-Hung; Lin, Jim Jr-Min

    2015-02-13

    Carbonyl oxides, or Criegee intermediates, are important transient species formed in the reactions of unsaturated hydrocarbons with ozone. Although direct detection of Criegee intermediates has recently been realized, the main atmospheric sink of Criegee intermediates remains unclear. We report ultraviolet absorption spectroscopic measurements of the lifetime of the simplest Criegee intermediate, CH2OO, at various relative humidity levels up to 85% at 298 kelvin. An extremely fast decay rate of CH2OO was observed at high humidity. The observed quadratic dependence of the decay rate on water concentration implied a predominant reaction with water dimer. On the basis of the water dimer equilibrium constant, the effective rate coefficient of the CH2OO + (H2O)2 reaction was determined to be 6.5 (±0.8) × 10(-12) cubic centimeters per second. This work would help modelers to better constrain the atmospheric concentrations of CH2OO.

  10. Field and Laboratory Studies of Reactions between Atmospheric Water Soluble Organic Acids and Inorganic Particles

    SciTech Connect

    Wang, Bingbing; Kelly, Stephen T.; Sellon, Rachel E.; Shilling, John E.; Tivanski, Alexei V.; Moffet, Ryan C.; Gilles, Mary K.; Laskin, Alexander

    2013-06-25

    Atmospheric inorganic particles undergo complex heterogeneous reactions that change their physicochemical properties. Depletion of chloride in sea salt particles was reported in previous field studies and was attributed to the acid displacement of chlorides with inorganic acids, such as nitric and sulfuric acids [1-2]. Recently, we showed that NaCl can react with water soluble organic acids (WSOA) and release gaseous hydrochloric acid (HCl) resulting in formation of organic salts [3]. A similar mechanism is also applicable to mixed WSOA/nitrate particles where multi-phase reactions are driven by the volatility of nitric acid. Furthermore, secondary organic material, which is a complex mixture of carboxylic acids, exhibits the same reactivity towards chlorides and nitrates. Here, we present a systematic study of reactions between atmospheric relevant WSOA, SOM, and inorganic salts including NaCl, NaNO3, and Ca(NO3)2 using complementary micro-spectroscopy analysis.

  11. Cluster Productions in Intermediate-Energy Proton-Nucleus Reactions

    SciTech Connect

    Iwamoto, Hiroki; Uozumi, Yusuke

    2008-04-17

    We propose a model to describe cluster productions within the framework of the intranuclear cascade (INC) model. In our model, combination of the 'surface coalescence' and the 'knockout' is implemented to describe cluster productions in intermediate-energy nuclear reactions. In the present work, the basic ingredients of our INC model are defined and applied to nucleon and cluster productions for the proton-nucleus reactions. Although our INC model has some difficulties and room for improvement, it gives a good overall agreement with experimental data of not only nucleon productions but also cluster productions at intermediate energies.

  12. PRODUCTS OF THE GAS-PHASE REACTIONS OF THE OH RADICAL WITH N-BUTYL METHYL ETHER AND 2-ISOPROPOXYETHANOL: REACTIONS OF ROC(O)< RADICALS. (R825252)

    EPA Science Inventory

    The products of the gas-phase reactions of the OH radical with n-butyl methyl ether and 2-isopropoxyethanol in the presence of NO have been investigated at 298 ? 2 K and 740 Torr total pressure of air by gas chromatography and in situ atmospheric pressure ionization...

  13. PRODUCTS OF THE GAS-PHASE REACTIONS OF THE OH RADICAL WITH N-BUTYL METHYL ETHER AND 2-ISOPROPOXYETHANOL: REACTIONS OF ROC(O)< RADICALS. (R825252)

    EPA Science Inventory

    The products of the gas-phase reactions of the OH radical with n-butyl methyl ether and 2-isopropoxyethanol in the presence of NO have been investigated at 298 ? 2 K and 740 Torr total pressure of air by gas chromatography and in situ atmospheric pressure ionization...

  14. Kinetics and products of the OH radical-initiated reaction of 3-methyl-2-butenal.

    PubMed

    Tuazon, Ernesto C; Aschmann, Sara M; Nishino, Noriko; Arey, Janet; Atkinson, Roger

    2005-06-07

    Kinetics and products of the gas-phase reaction of OH radicals with 3-methyl-2-butenal [(CH3)2C=CHCHO] have been investigated at room temperature and atmospheric pressure of air. Using a relative rate method with methacrolein as the reference compound, a rate constant for the reaction of OH radicals with 3-methyl-2-butenal of (6.21 +/- 0.18) x 10(-11) cm3 molecule(-1) s(-1) at 296 +/- 2 K was measured, where the indicated error does not include the uncertainty in the rate constant for the methacrolein reference compound. Products of this reaction were investigated using in situ Fourier transform infrared (FT-IR) spectroscopy and solid phase microextraction (SPME) fibers coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl compounds, with subsequent thermal desorption and analysis by gas chromatography. The products observed and the molar formation yields were: glyoxal, 40 +/- 3%; acetone, 74 +/- 6%; 2-hydroxy-2-methylpropanal, 4.6 +/- 0.7%; CO2, 39% initially, decreasing to 30% at greater extents of reaction; peroxyacyl nitrate(s) [RC(O)OONO2], 5-8%, increasing with the extent of reaction and with the sum of the CO2 and RC(O)OONO2 yields being 38 +/- 6%; and organic nitrates [RONO2], 8.5 +/- 2.3%. The formation of these products is readily explained by a reaction mechanism based on those previously formulated for the corresponding reactions of the alpha,beta-unsaturated aldehydes acrolein, crotonaldehyde and methacrolein. Based on the mechanism proposed, at room temperature H-atom abstraction from the CHO group accounts for 40 +/- 6% of the overall reaction, and OH radical addition to the carbon atoms of the C=C bond accounts for 53 +/- 4% of the overall reaction. Hence 93 +/- 8% of the reaction products and pathways are accounted for.

  15. Products of the Benzene + O(3P) Reaction

    SciTech Connect

    Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Meloni, Giovanni; Trevitt, Adam J.; Epifanovsky, Evgeny; Krylov, Anna I.; Sirjean, Baptiste; Dames, Enoch; Wang, Hai

    2009-12-21

    The gas-phase reaction of benzene with O(3P) is of considerable interest for modeling of aromatic oxidation, and also because there exist fundamental questions concerning the prominence of intersystem crossing in the reaction. While its overall rate constant has been studied extensively, there are still significant uncertainties in the product distribution. The reaction proceeds mainly through the addition of the O atom to benzene, forming an initial triplet diradical adduct, which can either dissociate to form the phenoxy radical and H atom, or undergo intersystem crossing onto a singlet surface, followed by a multiplicity of internal isomerizations, leading to several possible reaction products. In this work, we examined the product branching ratios of the reaction between benzene and O(3P) over the temperature range of 300 to 1000 K and pressure range of 1 to 10 Torr. The reactions were initiated by pulsed-laser photolysis of NO2 in the presence of benzene and helium buffer in a slow-flow reactor, and reaction products were identified by using the multiplexed chemical kinetics photoionization mass spectrometer operating at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory. Phenol and phenoxy radical were detected and quantified. Cyclopentadiene and cyclopentadienyl radical were directly identified for the first time. Finally, ab initio calculations and master equation/RRKM modeling were used to reproduce the experimental branching ratios, yielding pressure-dependent rate expressions for the reaction channels, including phenoxy + H, phenol, cyclopentadiene + CO, which are proposed for kinetic modeling of benzene oxidation.

  16. A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence. Ph.D. Thesis Catholic Univ. of America; [ammonia in the atmosphere of Jupiter

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.

    1982-01-01

    The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

  17. Atmospheric Chemistry of 1H-Heptafluorocyclopentene (cyc-CF2CF2CF2CF═CH-): Rate Constant, Products, and Mechanism of Gas-Phase Reactions with OH Radicals, IR Absorption Spectrum, Photochemical Ozone Creation Potential, and Global Warming Potential.

    PubMed

    Liu, Dongpeng; Qin, Sheng; Li, Wei; Zhang, Di; Guo, Zhikai

    2016-12-08

    The rate constant for gas-phase reactions of OH radicals with 1H-heptafluorocyclopentene (cyc-CF2CF2CF2CF═CH-) was measured using a relative rate method at 298 K: (5.20 ± 0.09) × 10(-14) cm(3) molecule(-1) s(-1). The quoted uncertainty includes two standard deviations from the least-squares regression, the systematic error from the GC analysis, and the uncertainties of the rate constants of the reference compounds. The OH-radical-initiated oxidation of cyc-CF2CF2CF2CF═CH- gives the main products COF2, CO, and CO2, leading to negligible environmental impact. For consumptions of cyc-CF2CF2CF2CF═CH- of less than 54%, the yield of the formation of ([COF2] + [CO] + [CO2])/5 (based on the conservation of carbon) was 0.99 ± 0.02, which is very close to 100%. A possible degradation mechanism was proposed. The radiative efficiency (RE) of cyc-CF2CF2CF2CF═CH- measured at room temperature was 0.215 W m(-2) ppb(-1). The atmospheric lifetime of cyc-CF2CF2CF2CF═CH- was calculated as 0.61 year, and the photochemical ozone creation potential (POCP) was negligible. The 20-, 100-, and 500-year time horizon global warming potentials (GWPs) were estimated as 153, 42, and 12, respectively.

  18. Making radioactive ion beams - Detecting reaction products

    NASA Astrophysics Data System (ADS)

    Raabe, Riccardo

    2016-10-01

    We present a didactical overview of the methods for the production of radioactive ion beams (RIBs), discussing the main characteristics and associated advantages and drawbacks of the in-flight separation and isotope separation on-line methods. We include a short overview of present and planned facilities, focusing on Europe. In the second part of the paper a brief introduction on the detection of radiation is given, followed by a discussion of the specific problems related to radiation detection in measurements involving RIBs. A few illustrative examples of detection setups are presented.

  19. Compression of Martian atmosphere for production of oxygen

    NASA Technical Reports Server (NTRS)

    Lynch, D. C.; Cutler, A. H.; Nolan, P. E.

    1991-01-01

    The compression of CO2 from the Martian atmosphere for production of O2 via an electrochemical cell is addressed. Design specifications call for an oxygen production rate of 10 kg per day and for compression of 50 times that mass of CO2. Those specifications require a compression rate of over 770 cfm at standard Martian temperature and pressure (SMTP). Much of the CO2 being compressed represents waste, unless it can be recycled. Recycling can reduce the volume of gas that must be compressed to 40 cfm at SMTP. That volume reduction represents significant mass savings in the compressor, heating equipment, filters, and energy source. Successful recycle of the gas requires separation of CO (produced in the electrochemical cell) from CO2, N2, and Ar found in the Martian atmosphere. That aspect was the focus of this work.

  20. The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

    NASA Astrophysics Data System (ADS)

    Müller, Jean-François; Liu, Zhen; Nguyen, Vinh Son; Stavrakou, Trissevgeni; Harvey, Jeremy N.; Peeters, Jozef

    2016-10-01

    Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of ~30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions.

  1. The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol.

    PubMed

    Müller, Jean-François; Liu, Zhen; Nguyen, Vinh Son; Stavrakou, Trissevgeni; Harvey, Jeremy N; Peeters, Jozef

    2016-10-17

    Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of ∼30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions.

  2. The reaction of methyl peroxy and hydroxyl radicals as a major source of atmospheric methanol

    PubMed Central

    Müller, Jean-François; Liu, Zhen; Nguyen, Vinh Son; Stavrakou, Trissevgeni; Harvey, Jeremy N.; Peeters, Jozef

    2016-01-01

    Methyl peroxy, a key radical in tropospheric chemistry, was recently shown to react with the hydroxyl radical at an unexpectedly high rate. Here, the molecular reaction mechanisms are elucidated using high-level quantum chemical methodologies and statistical rate theory. Formation of activated methylhydrotrioxide, followed by dissociation into methoxy and hydroperoxy radicals, is found to be the main reaction pathway, whereas methylhydrotrioxide stabilization and methanol formation (from activated and stabilized methylhydrotrioxide) are viable minor channels. Criegee intermediate formation is found to be negligible. Given the theoretical uncertainties, useful constraints on the yields are provided by atmospheric methanol measurements. Using a global chemistry-transport model, we show that the only explanation for the high observed methanol abundances over remote oceans is the title reaction with an overall methanol yield of ∼30%, consistent with the theoretical estimates given their uncertainties. This makes the title reaction a major methanol source (115 Tg per year), comparable to global terrestrial emissions. PMID:27748363

  3. Reaction of benzene with atomic carbon: pathways to fulvenallene and the fulvenallenyl radical in extraterrestrial atmospheres and the interstellar medium.

    PubMed

    da Silva, Gabriel

    2014-06-05

    The reaction of benzene with ground-state atomic carbon, C((3)P), has been investigated using the G3X-K composite quantum chemical method. A suite of novel energetically favorable pathways that lead to previously unconsidered products are identified. Reaction is initiated by barrierless C atom cycloaddition to benzene on the triplet surface, producing a vibrationally excited [C7H6]* adduct that can dissociate to the cycloheptatrienyl radical (+ H) via a relatively loose transition state 4.4 kcal mol(-1) below the reactant energies. This study also identifies that this reaction adduct can isomerize to generate five-membered ring intermediates that can further dissociate to the global C7H5 minima, the fulvenallenyl radical (+ H), or to c-C5H4 and acetylene, with limiting barriers around 20 and 10 kcal mol(-1) below the reactants, respectively. If intersystem crossing to the singlet surface occurs, isomerization pathways that are lower-yet in energy are available leading to the C7H6 minima fulvenallene, with all barriers over 40 kcal mol(-1) below the reactants. From here further barrierless fragmentation to fulvenallenyl + H can proceed at ca. 25 kcal mol(-1) below the reactants. In the reducing atmospheres of planets like Jupiter and satellites like Titan, where benzene and C((3)P) are both expected, it is proposed that fulvenallene and the fulvenallenyl radical would be the dominant products of the C6H6 + C((3)P) reaction. Fulvenallenyl may also be a significant reaction product under collision-free conditions representative of the interstellar medium, although further work is required here to confirm the identity of the C7H5 radical product.

  4. Gas-phase reaction of ( E)-β-farnesene with ozone: Rate coefficient and carbonyl products

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Bejan, Iustinian; Sodeau, John R.; Wenger, John C.

    The gas-phase ozonolysis of ( E)-β-farnesene was investigated in a 3.91 m 3 atmospheric simulation chamber at 296 ± 2 K and relative humidity of around 0.1%. The relative rate method was used to determine the reaction rate coefficient of (4.01 ± 0.17) × 10 -16 cm 3 molecule -1 s -1, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate coefficients for the reference compounds (γ-terpinene, cis-cyclooctene and 1,5-cyclooctadiene). Gas phase carbonyl products were collected using a denuder sampling technique and analyzed with GC/MS following derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA). The reaction products detected were acetone, 4-oxopentanal, methylglyoxal, 4-methylenehex-5-enal, 6-methylhept-5-en-2-one, and ( E)-4-methyl-8-methylenedeca-4,9-dienal. A detailed mechanism for the gas-phase ozonolysis of ( E)-β-farnesene is proposed, which accounts for all of the products observed in this study. The results of this work indicate that the atmospheric reaction of ( E)-β-farnesene with ozone has a lifetime of around 1 h and is another possible source of the ubiquitous carbonyls, acetone, 4-oxopentanal and 6-methylhept-5-en-2-one in the atmosphere.

  5. Application of an atmospheric pressure sampling mass spectrometer to chlorination reactions

    NASA Technical Reports Server (NTRS)

    Jacobson, N. S.

    1986-01-01

    An atmospheric pressure mass spectrometric sampling system, based on a free jet expansion was used to study certain M-Cl-O reactions at high temperatures. The apparatus enables the volatile species from a 1-atm chemical process to be directly identified with a mass spectrometer which operates at approx. 10 to the minus 8th power torr. Studies for both pure metals and alloys are discussed. It is shown that this mass spectrometer system aids in identifying the volatile species, and provides fundamental information on the reaction mechanism.

  6. The atmospheric degradation pathways of BrCH2O2: computational calculation on mechanisms of the reaction with HO2.

    PubMed

    Tang, Yizhen; Sun, Jingyu; Zhang, Yunju; Wang, Rongshun

    2014-09-01

    Mechanisms for the atmospheric degradation reaction of BrCH2O2+HO2 were investigated using quantum chemistry methods. The result indicates that the dominant product is BrCH2OOH+O2((3)Σ). While CH2O+HBr+O3, BrCHO+OH+HO2 and CH2O+Br+HO3 will be competitive to a certain extent in the atmosphere. Meanwhile, the nascent product - BrCH2OOH reacts easily with OH radicals leading to BrCH2O2 again under the atmospheric conditions. Moreover, OH radicals could act as a catalyst in the net reaction of BrCH2OOH→BrCHO+H2O. Thus the proposed product BrCHO+H2O+O2 in the experiment might be generated from the subsequent reaction of BrCH2OOH with extra OH radicals. Comparisons indicate that halogen substitution effect makes minor contributions to the XCH2O2 (X=H, F, Cl and Br)+HO2 reactions in the atmosphere. Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan's upper atmosphere and the interstellar medium.

    PubMed

    Wang, Zhe-Chen; Bierbaum, Veronica M

    2016-06-07

    The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

  8. Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan's upper atmosphere and the interstellar medium

    NASA Astrophysics Data System (ADS)

    Wang, Zhe-Chen; Bierbaum, Veronica M.

    2016-06-01

    The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

  9. Toxicity of aerosols of sodium reaction products.

    PubMed

    Zwicker, G M; Allen, M D; Stevens, D L

    1979-01-01

    Sodium is used as the heat transfer medium in several new energy technologies such as liquid-metal fast-breeder reactors and solar-thermal collection systems. Because sodium burns in air and reacts violently with water, the potential exists for an airborne release of sodium combustion products and subsequent human exposure. To help evaluate the potential short-term hazard from an accidental sodium fire, male juvenile or adult Wistar rats were exposed to sodium aerosols for 2 hours to determine the dose at which 50 percent of the animals were affected (ED50) for each age group. The estimated ED50 of 510 microgram/l for adults was not significantly different from the estimated ED50 of 489 microgram/l for juveniles. The incidence of acute laryngitis, attributed to exposure, was three times higher for juvenile rats than for adults, and the degree of severity of this lesion was significantly (P less than 0.05) higher for juveniles.

  10. A case of a single water molecule accelerating the atmospheric reactions of hydroxyl radical at temperatures near 200 K

    NASA Astrophysics Data System (ADS)

    Kaur, Ramanpreet; Vikas

    2017-10-01

    A single water molecule is known to significantly lower the potential energy barrier in the atmospheric reactions of hydroxyl radical with volatile organic compounds but except at extremely low temperatures, it has never been observed to accelerate the reactions investigated so far. This quantum-mechanical computational work reveals a probable case of observing a single water molecule accelerating the atmospheric reactions of Trifluoroacetic acid and Trifluoroacetaldehyde at temperatures near 200 K under tropospheric conditions.

  11. Reactions of SIV species with organic compounds: formation mechanisms of organo-sulfur derivatives in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Passananti, Monica; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; George, Christian

    2015-04-01

    Secondary organic aerosol (SOA) have an important impact on climate, air quality and human health. However the chemical reactions involved in their formation and growth are not fully understood or well-constrained in climate models. It is well known that inorganic sulfur (mainly in oxidation states (+IV) and (+VI)) plays a key role in aerosol formation, for instance sulfuric acid is known to be a good nucleating gas. In addition, acid-catalyzed heterogeneous reactions of organic compounds has shown to produce new particles, with a clear enhancement in the presence of ozone (Iinuma 2013). Organosulfates have been detected in tropospheric particles and aqueous phases, which suggests they are products of secondary organic aerosol formation process (Tolocka 2012). Originally, the production of organosulfates was explained by the esterification reaction of alcohols, but this reaction in atmosphere is kinetically negligible. Other formation pathways have been suggested such as hydrolysis of peroxides and reaction of organic matter with sulfite and sulfate radical anions (SO3-, SO4-) (Nozière 2010), but it remains unclear if these can completely explain atmospheric organo-sulfur aerosol loading. To better understand the formation of organo-sulfur compounds, we started to investigate the reactivity of SIV species (SO2 and SO32-) with respect to specific functional groups (organic acids and double bonds) on atmospherically relevant carboxylic acids and alkenes. The experiments were carried out in the homogeneous aqueous phase and at the solid-gas interface. A custom built coated-wall flow tube reactor was developed to control relativity humidity, SO2 concentration, temperature and gas flow rate. Homogeneous and heterogeneous reaction kinetics were measured and resulting products were identified using liquid chromatography coupled with an orbitrap mass spectrometer (LC-HR-MS). The experiments were performed with and without the presence of ozone in order to evaluate any

  12. Long-term elevated atmospheric CO2 enhances forest productivity

    NASA Astrophysics Data System (ADS)

    Loecke, T. D.; Groffman, P. M.; Treseder, K. K.; LaDeau, S.

    2011-12-01

    that warmer sites also promote tree growth. In- growth root cores, soil N mineralization and nitrification assays, and soil C and N contents all suggest that N is unlikely to be limiting current tree productivity on most sites across our rural to urban transect. Furthermore, soil lead content varied little across these forest sites, suggesting that heavy metal contamination is not likely a significant control on forest productivity in our study. These results lend support for the overarching hypothesis that terrestrial ecosystems will sequester more C under greater atmospheric CO2 concentrations and warmer air temperatures.

  13. Potential atmospheric production of small volatile organic compounds from soot oxidation

    NASA Astrophysics Data System (ADS)

    Horn, A.; Carpenter, L.; Daly, H.; Jones, C.

    2003-04-01

    In the polluted troposphere, VOCs are involved in a range of interlinked chemical and photochemical cycles with a direct bearing on the production of ozone. The rates of emission, production and reaction of VOC are therefore an important component of atmospheric models. Recent urban measurements using 2D-GC methods show that there are a large number of unidentified and unattributed VOC components. Any new sources of such material with high photochemical ozone creation potentials may therefore be significant. Hydrocarbon, fossil fuel and biomass burning produces particulate carbonaceous aerosols (soot) in addition to gas phase products. Soot in the atmosphere is known to undergo oxidation becoming hydrophilic in aged urban plumes and the process is also known to produce water soluble organic compounds. In our experiments, soot samples are prepared by combustion of appropriate liquid hydrocarbons and reacted with ozone in a glass reaction vessel. Analysis of the surface and gas-phase during the course of this reaction confirms kinetic measurements showing irreversible uptake of O_3 on soot and further identify that the reaction has oxidised the surface. Transmission electron micrographs of the fresh and ozonised soot reveal small, coagulated particles: fresh soot particle size ranges from 50--90 nm which reduces to 40--50 nm after ozonolysis. Separation of the soluble components of fresh and ozonised soot samples analysed by GC/MS reveal the presence of polyaromatic and unsaturated components in unreacted soot and partially oxidised components post-ozonolysis. ATR-IR spectra of soot extracts and ozonised soot confirm that surface features due to the creation of oxidised surface products grow in with exposure time. These include carbonyl, ester and alcohol functional groups. Direct sampling of the gas-phase during the ozone reaction allows some gaseous products to be identified as small organic acids, ketones and alcohols. Overall, the reaction of ozone with soot

  14. Molecular weight growth in Titan's atmosphere: Branching pathways for the reaction of 1-propynyl radical (H3CC≡C˙) with small alkenes and alkynes

    DOE PAGES

    Kirk, Benjamin B.; Savee, John D.; Trevitt, Adam J.; ...

    2015-07-16

    The reaction of small hydrocarbon radicals (i.e. ˙CN, ˙C2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC≡C˙), a likely product from the high-energymore » photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (–H = 27%, –CH3 = 73%) and (–H = 14%, –CH3 = 86%), respectively. Altogether, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.« less

  15. Molecular weight growth in Titan's atmosphere: branching pathways for the reaction of 1-propynyl radical (H3CC≡C˙) with small alkenes and alkynes.

    PubMed

    Kirk, Benjamin B; Savee, John D; Trevitt, Adam J; Osborn, David L; Wilson, Kevin R

    2015-08-28

    The reaction of small hydrocarbon radicals (i.e.˙CN, ˙C2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC[triple bond, length as m-dash]C˙), a likely product from the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (-H = 27%, -CH3 = 73%) and (-H = 14%, -CH3 = 86%), respectively. Together, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.

  16. Molecular weight growth in Titan's atmosphere: Branching pathways for the reaction of 1-propynyl radical (H3CC≡C˙) with small alkenes and alkynes

    SciTech Connect

    Kirk, Benjamin B.; Savee, John D.; Trevitt, Adam J.; Osborn, David L.; Wilson, Kevin R.

    2015-07-16

    The reaction of small hydrocarbon radicals (i.e. ˙CN, ˙C2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC≡C˙), a likely product from the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (–H = 27%, –CH3 = 73%) and (–H = 14%, –CH3 = 86%), respectively. Altogether, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.

  17. Adsorption and reactions of atmospheric constituents and pollutants on ice particles: an FTIR study

    NASA Astrophysics Data System (ADS)

    Rudakova, A. V.; Marinov, I. L.; Poretskiy, M. S.; Tsyganenko, A. A.

    2009-04-01

    , which act as adsorption sites either as a proton-donor or as a donor of the lone pair of electrons. Such adsorption-induced relaxation explains the dependence of physico-chemical properties of icy particles on the presence of atmospheric gases. Spectra HCN/D2O and ND3/D2O mixed icy films with low (1:10) dopant/water ratios do not manifest any changes in the acidic or basic properties of dangling hydroxyl groups or surface oxygen atoms, but reveal a difference in the proportion between the concentrations of these sites as compared with that for pure water ice. For high dopant concentrations (1:1), the dangling hydroxyls were not observed; the dominant adsorption sites for CO are likely to be the unsaturated oxygen atoms, while serious structural changes occur in the bulk of ices. Ecologically important reactions of atmospheric pollutants such as ozonolysis of ethene, chlorinated ethenes, hydrogen cyanide, and methyl bromide adsorbed on water ice film as well as the influence of UV radiation on this process have been studied in 77 - 200 K temperature range by FTIR spectroscopy. Ozone co-adsorption with ethene or C2H3Cl readily leads to ozonolysis reaction, which also starts for C2H2Cl2 isomers but only at temperatures elevated up to 120 - 150 K. Co-adsorption of O3 with HCN or CH3Br molecules in the dark does not lead to any noticeable spectral changes. Irradiation of HCN or CH3Br deposited on ice films in the presence of ozone leads to appearance of new bands revealing the formation of ozonolysis products. The same "synergetic effect" of simultaneous action of ozone and UV radiation at 77 K, was found for C2H2Cl2 isomers and C2Cl4, which are resistant against O3 even at higher temperatures. The obtained spectral dependence of photo-ozonolysis of C2Cl4 and HCN at 77 K shows that photoexcitation or photodissociation of ozone, evidently, accounts for the observed processes. The surface of ice particles, thus, plays the role of a condenser of atmospheric pollutants and acts

  18. Atmospheric reaction systems as null-models to identify structural traces of evolution in metabolism.

    PubMed

    Holme, Petter; Huss, Mikael; Lee, Sang Hoon

    2011-05-06

    The metabolism is the motor behind the biological complexity of an organism. One problem of characterizing its large-scale structure is that it is hard to know what to compare it to. All chemical reaction systems are shaped by the same physics that gives molecules their stability and affinity to react. These fundamental factors cannot be captured by standard null-models based on randomization. The unique property of organismal metabolism is that it is controlled, to some extent, by an enzymatic machinery that is subject to evolution. In this paper, we explore the possibility that reaction systems of planetary atmospheres can serve as a null-model against which we can define metabolic structure and trace the influence of evolution. We find that the two types of data can be distinguished by their respective degree distributions. This is especially clear when looking at the degree distribution of the reaction network (of reaction connected to each other if they involve the same molecular species). For the Earth's atmospheric network and the human metabolic network, we look into more detail for an underlying explanation of this deviation. However, we cannot pinpoint a single cause of the difference, rather there are several concurrent factors. By examining quantities relating to the modular-functional organization of the metabolism, we confirm that metabolic networks have a more complex modular organization than the atmospheric networks, but not much more. We interpret the more variegated modular arrangement of metabolism as a trace of evolved functionality. On the other hand, it is quite remarkable how similar the structures of these two types of networks are, which emphasizes that the constraints from the chemical properties of the molecules has a larger influence in shaping the reaction system than does natural selection.

  19. Atmospheric Reaction Systems as Null-Models to Identify Structural Traces of Evolution in Metabolism

    PubMed Central

    Holme, Petter; Huss, Mikael; Lee, Sang Hoon

    2011-01-01

    The metabolism is the motor behind the biological complexity of an organism. One problem of characterizing its large-scale structure is that it is hard to know what to compare it to. All chemical reaction systems are shaped by the same physics that gives molecules their stability and affinity to react. These fundamental factors cannot be captured by standard null-models based on randomization. The unique property of organismal metabolism is that it is controlled, to some extent, by an enzymatic machinery that is subject to evolution. In this paper, we explore the possibility that reaction systems of planetary atmospheres can serve as a null-model against which we can define metabolic structure and trace the influence of evolution. We find that the two types of data can be distinguished by their respective degree distributions. This is especially clear when looking at the degree distribution of the reaction network (of reaction connected to each other if they involve the same molecular species). For the Earth's atmospheric network and the human metabolic network, we look into more detail for an underlying explanation of this deviation. However, we cannot pinpoint a single cause of the difference, rather there are several concurrent factors. By examining quantities relating to the modular-functional organization of the metabolism, we confirm that metabolic networks have a more complex modular organization than the atmospheric networks, but not much more. We interpret the more variegated modular arrangement of metabolism as a trace of evolved functionality. On the other hand, it is quite remarkable how similar the structures of these two types of networks are, which emphasizes that the constraints from the chemical properties of the molecules has a larger influence in shaping the reaction system than does natural selection. PMID:21573072

  20. Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

    PubMed

    Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

    2015-02-17

    CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on

  1. The Hydroxyl Radical Reaction Rate Constant and Products of Cyclohexanol

    DTIC Science & Technology

    2007-10-01

    atmospheric degradation mechanism. The observed products and their formation yields were: cyclohexanone (0.55 0.06), hexanedial (0.32 0.15), 3...COL, tridecane, and decane were obtained from Aldrich with a purity of 99%. Pentanal (99%) and cyclohexanone (99%) were purchased through Ultra... Cyclohexanone (CON) was the only OH COL re- action product observed during the initial kinetic ex- periments. Its presence was also detected later using

  2. Does atmospheric deposition support phytoplankton productivity in Monterey Bay, CA?

    NASA Astrophysics Data System (ADS)

    Mazloom, S.; Mackey, K. R.; Paytan, A.

    2008-12-01

    Aerosol deposition has been shown to enhance phytoplankton productivity in nutrient-deplete open ocean environments, by providing phosphorus and iron to stimulate production in general and nitrogen fixation in particular. This project was designed to determine the importance of atmospheric aerosol deposition's ability to support phytoplankton in Monterey Bay, a productive upwelling region, and in waters surrounding coastal California. To conduct this experiment, MODIS satellite images of the Bay were taken from the years 2002- 2008 and were then grouped into eight day time intervals. The three factors tested in the experiment were correlations between sea surface temperature, the amount of aerosol (as determined by optical thickness), and the amount of chlorophyll. Aerosols correlated positively with chlorophyll concentrations offshore of Monterey Bay in the summer, but not within the Bay itself. No significant correlations were found for any locations in the winter months. The trends found in the experiment will be shown and the importance of atmospheric aerosol in supporting phytoplankton production in Monterey Bay will be highlighted.

  3. Particulate and gas-phase products from the atmospheric degradation of chlorpyrifos and chlorpyrifos-oxon

    NASA Astrophysics Data System (ADS)

    Borrás, Esther; Ródenas, Milagros; Vázquez, Mónica; Vera, Teresa; Muñoz, Amalia

    2015-12-01

    The phosphorothioate structure is highly present in several pesticides. However, there is a lack of information about its degradation process in air and the secondary pollutants formed. Herein, the atmospheric reactions of chlorpyrifos, one of the most world-used insecticide, and its main degradation product - chlorpyrifos-oxon - are described. The photo-oxidation under the presence of NOx was studied in a large outdoor simulation chamber for both chlorpyrifos and chlorpyrifos-oxon, observing a rapid degradation (Half lifetime < 3.5 h for both compounds). Also, the photolysis reactions of both were studied. The formation of particulate matter (aerosol mass yield ranged 6-59%) and gaseous products were monitored. The chemical composition of minor products was studied, identifying 15 multi-oxygenated derivatives. The most abundant products were ring-retaining molecules such as 3,5,6-trichloropyridin-2-ol and ethyl 3,5,6-trichloropyridin-2-yl hydrogen phosphate. An atmospheric degradation mechanism has been amplified based on an oxidation started with OH-nucleophilic attack to Pdbnd S bond.

  4. Ambient reaction kinetics of atmospheric oxygenated organics with the OH radical: a computational methodology study.

    PubMed

    Elm, Jonas; Jørgensen, Solvejg; Bilde, Merete; Mikkelsen, Kurt V

    2013-06-28

    The gas phase hydrogen abstraction reaction kinetics of short chained oxygenated hydrocarbons of atmospheric relevance has been studied using density functional theory, basis set extrapolation procedures, Møller-Plesset second order perturbation theory and Coupled-Cluster Singles Doubles. The rate constants for the reaction of the OH radical with nine different oxygenated compounds: CH3OH, CH3CH2OH, H2CO, CH3CHO, CH3COCH3, CH3OCH3, HCOOH, CH3COOH, HCOOCH3 with a total of 18 individual hydrogen abstraction reactions have been computationally determined and compared to experimental data. The performance of DFT in predicting the imaginary vibrational frequency of the nuclear motion at the transition state has been evaluated to assess tunnelling effects using Wigner, Bell and Eckart tunnelling corrections. Several different hybrid methodologies utilizing DFT/MP2 structures, vibrational frequencies and explicitly correlated Coupled Cluster single point energy corrections have been investigated to identify an approach for obtaining reliable reaction kinetics. Our investigation shows that CCSD(T)-F12a/VTZ-F12//BH&HLYP/aug-cc-pVTZ using a Bell or Eckart tunnelling correction yields rate constants within a factor of ~3 of experimental data and branching ratios within experimental uncertainty for the test set of short chained oxygenated compounds of atmospheric relevance.

  5. Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry.

    PubMed

    Osborn, David L

    2017-03-15

    Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges. Expected final online publication date for the Annual Review of Physical Chemistry Volume 68 is April 20, 2017. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

  6. α-Terpineol reactions with the nitrate radical: Rate constant and gas-phase products

    NASA Astrophysics Data System (ADS)

    Jones, Brian T.; Ham, Jason E.

    The bimolecular rate constant of k rad +α-terpineol (16 ± 4) × 10 -12 cm 3 molecule -1 s -1 was measured using the relative rate technique for the reaction of the nitrate radical (NO 3rad ) with α-terpineol (2-(4-methyl-1-cyclohex-3-enyl)propan-2-ol) at 297 ± 3 K and 1 atmosphere total pressure. To more clearly define part of α-terpineol's indoor environment degradation mechanism, the products of α-terpineol + NO 3rad reaction were investigated. The identified reaction products were: acetone, glyoxal (HC( dbnd O)C( dbnd O)H), and methylglyoxal (CH 3C( dbnd O)C( dbnd O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N, O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose the other major reaction products: 6-hydroxyhept-5-en-2-one, 4-(1-hydroxy-1-methylethyl)-1-methyl-2-oxocyclohexyl nitrate, 5-(1-hydroxy-1-methylethyl)-2-oxocyclohexyl nitrate, 1-formyl-5-hydroxy-4-(hydroxymethyl)-1,5-dimethylhexyl nitrate, and 1,4-diformyl-5-hydroxy-1,5-dimethylhexyl nitrate. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible α-terpineol + NO 3rad reaction mechanisms based on previously published volatile organic compound + NO 3rad gas-phase mechanisms. The additional gas-phase products (2,6,6-trimethyltetrahydro-2 H-pyran-2,5-dicarbaldehyde and 2,2-dimethylcyclohexane-1,4-dicarbaldehyde) are proposed to be the result of cyclization through a reaction intermediate.

  7. Effect of atmospheric oxidative plasma treatments on polypropylenic fibers surface: Characterization and reaction mechanisms

    NASA Astrophysics Data System (ADS)

    Nisticò, Roberto; Magnacca, Giuliana; Faga, Maria Giulia; Gautier, Giovanna; D'Angelo, Domenico; Ciancio, Emanuele; Lamberti, Roberta; Martorana, Selanna

    2013-08-01

    Atmospheric pressure plasma-dielectric barrier discharge (APP-DBD, open chamber configuration) was used to functionalize polypropylene (PP) fibers surface in order to generate oxidized-reactive groups such as hydroperoxides, alcohols and carbonyl species (i.e. ketones and others). Such a species increased the surface polarity, without causing material degradation. Three different types of plasma mixture (He, He/O2, He/O2/H2O) under three different values of applied power (750, 1050, 1400 W) were investigated. The formed plasma species (O2+, O single atom and OH radical) and their distribution were monitored via optical emission spectrometry (OES) measurements, and the plasma effects on PP surface species formation were followed by X-ray photoemission spectroscopy (XPS). Results allowed to better understand the reaction pathways between plasma phase and PP fibers. In fact, two reaction mechanisms were proposed, the first one concerning the plasma phase reactions and the second one involving material surface modifications.

  8. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of alkylphenyl... Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl dibenzene... identified generically as reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and...

  9. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl...

  10. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylphenyl... Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl dibenzene... identified generically as reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and...

  11. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl...

  12. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of alkylphenyl... Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl dibenzene... identified generically as reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and...

  13. 40 CFR 721.10448 - Acetic acid, hydroxy- methoxy-, methyl ester, reaction products with substituted alkylamine...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... ester, reaction products with substituted alkylamine (generic). 721.10448 Section 721.10448 Protection... Acetic acid, hydroxy- methoxy-, methyl ester, reaction products with substituted alkylamine (generic). (a... generically as acetic acid, hydroxymethoxy-, methyl ester, reaction products with substituted alkylamine...

  14. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl...

  15. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl...

  16. 40 CFR 721.10679 - Carboxylic acid, substituted alkylstannylene ester, reaction products with inorganic acid tetra...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... alkylstannylene ester, reaction products with inorganic acid tetra alkyl ester (generic). 721.10679 Section 721... Carboxylic acid, substituted alkylstannylene ester, reaction products with inorganic acid tetra alkyl ester... identified generically as carboxylic acid, substituted alkylstannylene ester, reaction products...

  17. 40 CFR 721.10448 - Acetic acid, hydroxy- methoxy-, methylester, reaction products with substituted alkylamine...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-, methylester, reaction products with substituted alkylamine (generic). 721.10448 Section 721.10448 Protection... Acetic acid, hydroxy- methoxy-, methylester, reaction products with substituted alkylamine (generic). (a... generically as acetic acid, hydroxymethoxy-, methyl ester, reaction products with substituted alkylamine...

  18. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl...

  19. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylphenyl... Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl dibenzene... identified generically as reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and...

  20. 40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of alkylphenyl... Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl dibenzene... identified generically as reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and...

  1. Radical product yields from the ozonolysis of short chain alkenes under atmospheric boundary layer conditions.

    PubMed

    Alam, Mohammed S; Rickard, Andrew R; Camredon, Marie; Wyche, Kevin P; Carr, Timo; Hornsby, Karen E; Monks, Paul S; Bloss, William J

    2013-11-27

    The gas-phase reaction of ozone with unsaturated volatile organic compounds (VOCs), alkenes, is an important source of the critical atmospheric oxidant OH, especially at night when other photolytic radical initiation routes cannot occur. Alkene ozonolysis is also known to directly form HO2 radicals, which may be readily converted to OH through reaction with NO, but whose formation is poorly understood. We report a study of the radical (OH, HO2, and RO2) production from a series of small alkenes (propene, 1-butene, cis-2-butene, trans-2-butene, 2-methylpropene, 2,3-dimethyl-2-butene (tetramethyl ethene, TME), and isoprene). Experiments were performed in the European Photoreactor (EUPHORE) atmospheric simulation chamber, with OH and HO2 levels directly measured by laser-induced fluorescence (LIF) and HO2 + ΣRO2 levels measured by peroxy-radical chemical amplification (PERCA). OH yields were found to be in good agreement with the majority of previous studies performed under comparable conditions (atmospheric pressure, long time scales) using tracer and scavenger approaches. HO2 yields ranged from 4% (trans-2-butene) to 34% (2-methylpropene), lower than previous experimental determinations. Increasing humidity further reduced the HO2 yields obtained, by typically 50% for an RH increase from 0.5 to 30%, suggesting that HOx production from alkene ozonolysis may be lower than current models suggest under (humid) ambient atmospheric boundary layer conditions. The mechanistic origin of the OH and HO2 production observed is discussed in the context of previous experimental and theoretical studies.

  2. Studies in photochemical smog chemistry. I. Atmospheric chemistry of toluene. II. Analysis of chemical reaction mechanisms for photochemical smog

    SciTech Connect

    Leone, J.A.

    1985-01-01

    This study focuses on two related topics in the gas phase organic chemistry of importance in urban air pollution. Part I describes an experimental and modeling effort aimed at developing a new explicit reaction mechanism for the atmospheric photooxidation of toluene. This mechanism is tested using experimental data from both indoor and outdoor smog chamber facilities. The predictions of the new reaction mechanism are found to be in good agreement with both sets of experimental data. Additional simulations performed with the new mechanism are used to investigate various mechanistic paths, and to gain insight into areas where the understanding is not complete. The outdoor experimental facility, which was built to provide the second set of experimental data, consists of a 65 cubic meter teflon smog chamber together with full instrumentation capable of measuring ozone, nitrogen dioxide, nitric oxide, peroxyacetyl nitrate (PAN), carbon monoxide, relative humidity, temperature, aerosol size distributions, and of course toluene and its photooxidation products. In Part II, a theoretical analysis of lumped chemical reaction mechanisms for photochemical smog is presented. Included is a description of a new counter species analysis technique which can be used to analyze any complex chemical reaction mechanism. Finally, a new lumped mechanism for photochemical smog is developed and tested against experimental data from two smog chamber facilities. Advantages of this mechanism relative to the existing lumped mechanisms are discussed.

  3. The Sentinel-4 Mission: Instrument Description and Atmospheric Composition Products

    NASA Astrophysics Data System (ADS)

    Veihelmann, Ben; Meijer, Yasjka; Ingmann, Paul; Koopman, Rob; Bazalgette Courrèges-Lacoste, Grégory; Stark, Hendrik

    2013-04-01

    The Sentinel-4 mission, together with Sentinel-5 and the Sentinel-5 Precursor missions, is part of the Global Monitoring for Environment and Security (GMES) space component covering the Earth's atmosphere. The primary objective of the Sentinel-4 mission is the observation of the diurnal cycle of tropospheric species in support of the air quality applications of GMES Atmosphere Services. The presentation focuses on the Sentinel-4/UVN instrument and its related Level-2 atmospheric composition products. The Sentinel-4 instrument is an Ultra-violet Visible Near infrared spectrometer (S4/UVN) which is embarked on the geostationary Meteosat Third Generation-Sounder (MTG-S) platforms. Key features of the S4/UVN instrument are the spectral range from 305 nm to 500 nm with a spectral resolution of 0.5 nm, and from 750 nm to 775 nm with a spectral resolution of 0.12 nm, in combination with a low polarization sensitivity and a high radiometric accuracy. The instrument shall observe Europe with a revisit time of one hour. The spatial sampling distance varies across the geographic coverage area and takes a value of 8 km at a reference location at 45˚ N. The expected launch date of the first MTG-S platform is 2019, and the expected lifetime is 15 years (two S4/UVN instruments in sequence on two MTG-S platforms). ESA will develop products based on the S4/UVN measurements for the key target species, which are NO2, O3, HCHO, SO2, aerosols, and CHOCHO, and for cloud and surface properties (mainly intermediate products). Also a synergetic O3 vertical profile product is foreseen based on observations from the S4/UVN and the MTG InfraRed Sounder (IRS) on-board the same platform. Synergetic aerosol and cloud products are foreseen based on observations from the S4/UVN and from the MTG Flexible Combined Imager (FCI) on-board the MTG-Imager (MTG-I) platform. Current pre-development studies are dedicated to a daily surface reflectance map product that treats the surface directionality as

  4. Spectroscopic Characterization of the Reaction Products Between HCl and the Simplest Criegee Intermediate CH_{2}OO

    NASA Astrophysics Data System (ADS)

    Cabezas, Carlos; Endo, Yasuki

    2017-06-01

    Carbonyl oxides (R_{1}R_{2}COO), also known as Criegee intermediates (CIs), react quickly with many trace atmospheric gases, including inorganic gases such as HCl, which are present in polluted urban atmospheres. A theoretical investigation of the reaction between the simplest CI, CH_{2}OO, with HCl suggests the formation of chloromethyl hydroperoxide (CMHP) through an insertion mechanism. To gain some insight, we have interrogated the reaction system containing CH_{2}OO and HCl through pure rotational spectroscopy. In our experiment, CH_{2}OO molecules have been generated in the discharged plasma of a CH_{2}I_{2}/O_{2} mixture, which containg a small amount of HCl enough to react with CH_{2}OO. The resulting products (including CH_{2}OO) were characterized by Fourier-transform microwave (FTMW) spectroscopy. Rotational transitions in the 6-40 GHz frequency range were observed by FTMW spectroscopy together with FTMW-mmW and MW-MW double-resonance techniques. The observed species was identified with the help of quantum chemical calculations as the most stable conformer of CMHP. The non observation of other different reaction products together with the absence of spectral features of the complex between HCl and CH_{2}OO enable us to understand the pathway of the HCl+CH_{2}OO reaction.

  5. Gas Sensor Evaluations in Polymer Combustion Product Atmospheres

    NASA Technical Reports Server (NTRS)

    Delgado, Rafael H.; Davis, Dennis D.; Beeson, Harold D.

    1999-01-01

    Toxic gases produced by the combustion or thermo-oxidative degradation of materials such as wire insulation, foam, plastics, or electronic circuit boards in space shuttle or space station crew cabins may pose a significant hazard to the flight crew. Toxic gas sensors are routinely evaluated in pure gas standard mixtures, but the possible interferences from polymer combustion products are not routinely evaluated. The NASA White Sands Test Facility (WSTF) has developed a test system that provides atmospheres containing predetermined quantities of target gases combined with the coincidental combustion products of common spacecraft materials. The target gases are quantitated in real time by infrared (IR) spectroscopy and verified by grab samples. The sensor responses are recorded in real time and are compared to the IR and validation analyses. Target gases such as carbon monoxide, hydrogen cyanide, hydrogen chloride, and hydrogen fluoride can be generated by the combustion of poly(vinyl chloride), polyimide-fluoropolymer wire insulation, polyurethane foam, or electronic circuit board materials. The kinetics and product identifications for the combustion of the various materials were determined by thermogravimetric-IR spectroscopic studies. These data were then scaled to provide the required levels of target gases in the sensor evaluation system. Multisensor toxic gas monitors from two manufacturers were evaluated using this system. In general, the sensor responses satisfactorily tracked the real-time concentrations of toxic gases in a dynamic mixture. Interferences from a number of organic combustion products including acetaldehyde and bisphenol-A were minimal. Hydrogen bromide in the products of circuit board combustion registered as hydrogen chloride. The use of actual polymer combustion atmospheres for the evaluation of sensors can provide additional confidence in the reliability of the sensor response.

  6. Atmospheric chemistry of 2-aminoethanol (MEA): reaction of the NH2(•)CHCH2OH radical with O2.

    PubMed

    da Silva, Gabriel

    2012-11-15

    The alkanolamine 2-aminoethanol (NH(2)CH(2)CH(2)OH), otherwise known as monoethanolamine (MEA), is a widely used solvent for carbon capture, yet relatively little is known about its atmospheric chemistry. The hydroxyl radical initiated oxidation of MEA is thought to predominantly form the α-aminoalkyl radical NH(2)(•)CHCH(2)OH, which will subsequently react with O(2) in the atmosphere to produce a peroxyl radical. We have investigated the reaction of O(2) with the NH(2)(•)CHCH(2)OH radical using quantum chemical calculations and master equation kinetic modeling. This reaction is found to proceed predominantly via a chemically activated mechanism under tropospheric conditions to directly produce the imine 2-iminoethanol (NH═CHCH(2)OH) + HO(2)(•), with lesser amounts of the collisionally deactivated peroxyl radical NH(2)CH(O(2)(•))CH(2)OH. By largely bypassing a peroxyl radical intermediate, this process avoids ozone-promoting conversion of NO to NO(2) and makes the oxidation of MEA to 2-iminoethanol HO(x)-neutral overall. The imine product of MEA oxidation is proposed as an important intermediate in the formation of aerosols via uptake to water droplets and subsequent hydrolysis to ammonia and glycolaldehyde.

  7. Validation of atmospheric VOC measurements by proton-transfer-reaction mass spectrometry using a gas-chromatographic preseparation method.

    PubMed

    Warneke, Carsten; De Gouw, Joost A; Kuster, William C; Goldan, Paul D; Fall, Ray

    2003-06-01

    Proton-transfer-reaction mass spectrometry (PTR-MS) has emerged as a useful tool to study volatile organic compounds (VOCs) in the atmosphere. In PTR-MS, proton-transfer reactions with H30+ ions are used to ionize and measure VOCs in air with a high sensitivity and fast time response. Only the masses of the ionized VOCs and their fragments, if any, are determined, and these product ions are not unique indicators of VOC identities. Here, a combination of gas chromatography and PTR-MS (GC-PTR-MS) is used to validate the measurements by PTR-MS of a number of common atmospheric VOCs. We have analyzed 75 VOCs contained in standard mixtures by GC-PTR-MS, which allowed detected masses to be unambiguously related to a specific compound. The calibration factors for PTR-MS and GC-PTR-MS were compared and showed that the loss of VOCs in the sample acquisition and GC system is small. GC-PTR-MS analyses of 56 air samples from an urban site were used to address the specificity of PTR-MS in complex air masses. It is demonstrated that the ions associated with methanol, acetonitrile, acetaldehyde, acetone, benzene, toluene, and higher aromatic VOCs are free from significant interference. A quantitative intercomparison between PTR-MS and GC-PTR-MS measurements of the aforementioned VOCs was performed and shows that they are accurately measured by PTR-MS.

  8. Modeling of atmospheric OH reaction rates using newly developed variable distance weighted zero order connectivity index

    NASA Astrophysics Data System (ADS)

    Markelj, Jernej; Pompe, Matevž

    2016-04-01

    A new variable distance weighted zero order connectivity index was used for development of structure-activity relationship for modeling reactivity of OH radical with alkanes and non-conjugated alkenes in the atmosphere. The proposed model is based on the assumptions that the total reaction rate can be obtained by summing all partial reaction rates and that all reaction sites are interrelated by influencing each other. The results suggest that these assumptions are justified. The model was compared with the EPA implemented model in the studied application domain and showed superior prediction capabilities. Further, optimized values of the weights that were used in our model permit some insight into mechanisms that govern the reaction OH + alkane/alkene. The most important conclusion is that the branching degree of the forming radical seems to play a major role in site specific reaction rates. Relative qualitative structural interpretation is possible, e.g. allylic site is suggested to be much more reactive than even tertiary sp3 carbon. Novel modeling software MACI, which was developed in our lab and is now available for research purposes, was used for calculations. Various variable topological indices that are again starting to be recognized because of their great potentials in simplicity, fast calculations, very good correlations and structural information, were implemented in the program.

  9. Atmospheric degradation of saturated alcohols: Room temperature rate coefficients for NO3 radical reactions

    NASA Astrophysics Data System (ADS)

    Moreno, Alberto; Salgado, Sagrario; Taccone, Raul; Martín, Pilar; Cabañas, Beatriz

    2014-10-01

    Rate coefficients for the reactions of NO3 radicals with a series of saturated alcohols are reported here using the relative rate technique. Experiments were performed using air as bath gas in a 50 L glass-pyrex reaction chamber at room temperature (298 ± 2) K with long-path FTIR spectroscopy used to monitor the reaction at atmospheric pressure (708 ± 8) Torr. The reference compounds used and their rate coefficients are: propanal kNO3 = (6.0 ± 0.6) × 10-15, methyl methacrylate kNO3 = (3.55 ± 0.62) × 10-15, acetaldehyde kNO3 = (2.62 ± 0.29) × 10-15 and propene kNO3 = (9.50 ± 1.9) × 10-15, in cm3 molecule-1 s-1. Rate coefficients obtained were (in units cm3 molecule-1 s-1): (1.87 ± 0.14) × 10-15, (2.39 ± 0.20) × 10-15, (2.28 ± 0.17) × 10-15, (1.80 ± 0.13) × 10-15 and (3.52 ± 0.19) × 10-15 for 1-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3,3-dimethyl-1-butanol and 3,3-dimethyl-2-butanol respectively. Reactivity trend can be explained in terms of the different types of hydrogen inside the hydrocarbon chain. The reaction occurs by an initial H-atom abstraction mainly from C-H groups of the alcohols by the NO3 radical being NO3 more reactive towards an H atom attached to a tertiary carbon than that attached to a secondary or primary carbon. Reactivity trend is compared with their similar structural 2-butanol and with the corresponding alkanes. Atmospheric implications are also discussed calculating lifetimes of the saturated alcohols studied here due to the reaction with NO3 radicals in comparison to their reactions with the other major atmospheric oxidants.

  10. The characterization of coal liquefaction products obtained under an inert atmosphere and catalytic conditions. Part II: Soluble products

    SciTech Connect

    Karaca, H.

    2006-03-15

    Beypazari and Tuncbilek lignite were liquefied using two different catalyst methods physically mixing and impregnation. The liquefaction occurred under conditions of inert atmosphere and various process parameters. Solvent to coal ratio, pressure, catalyst type, catalyst concentration, temperature, and time were examined as process parameters. The most appropriate parameters for the total soluble products obtained by liquefaction of both lignites and for elemental analysis of preasphaltenes were determined as follows: 2/1 solvent to coal ratio; from 1.25 MPa to 2.50 MPa initial nitrogen pressure; Fe{sub 2}O{sub 3} and Mo(CO){sub 6} as catalyst types; 3% as catalyst concentration; 400{sup o}C as reaction temperature; and 60 min as reaction time. In general, fuel quality of both preasphaltene and total soluble products decreased as temperature increased above 400{sup o}C and reaction time exceeded 60 min. The fuel quality of the preasphaltenes and the total soluble products obtained under the catalytic conditions and in the state of impregnation of catalyst onto coal is higher than under the noncatalytic conditions and in the state of physically mixing of catalyst.

  11. Gasdynamic propagation of rocket exhaust products in the upper atmosphere

    NASA Astrophysics Data System (ADS)

    Molchanov, A. G.; Platov, Yu. V.

    2011-12-01

    The dispersion of exhaust products of rocket fuel in the direction perpendicular to the motion of a rocket is investigated in this work. A comparison of the results of numerical calculations with a self-similar approximation of a strong cylindrically symmetric explosion is fulfilled. It is shown that at sufficiently high rocket velocity V ∞, which exceeds the sum of gas exhaust velocity V e from the nozzle and sound speed V s ( V ∞ > V e + V s ), a gasdynamic hole can arise around the rocket trajectory in the upper atmosphere, inside which the total concentration of gas becomes less than the equilibrium concentration of gas at a given altitude. The dynamics of the profiles of density and temperature of the exhaust products inside a rocket plume is calculated.

  12. Gas-Phase Reactions of Methoxyphenols with NO3 Radicals: Kinetics, Products, and Mechanisms.

    PubMed

    Zhang, Haixu; Yang, Bo; Wang, Youfeng; Shu, Jinian; Zhang, Peng; Ma, Pengkun; Li, Zhen

    2016-03-03

    Methoxyphenols, a group of important tracers for wood smoke, are emitted to the atmosphere in large quantities, but their transformations are rarely studied. In this study, the kinetics and products of the gas-phase reactions of eugenol and 4-ethylguaiacol with NO3 radicals were investigated online using a vacuum ultraviolet photoionization gas time-of-flight mass spectrometer. The rate coefficients of the gaseous reactions of eugenol and 4-ethylguaiacol with NO3 radicals were (1.6 ± 0.4) × 10(-13) and (1.1 ± 0.2) × 10(-12) cm(3) molecule(-1) s(-1) (at 298 K), indicating that the atmospheric lifetimes of the NO3 radicals were 3.5 and 0.5 h, respectively. With the aid of gas-chromatography-mass-spectrometry analysis, several types of degradation products were identified with nitro derivatives as the major products. The configurations of the nitro-product isomers and their formation mechanisms were determined via theoretical calculations. On the basis of these products, degradation pathways of the methoxyphenols with NO3 radicals were proposed. This study determines the degradation rates and mechanisms of the methoxyphenols at night and implies the significant NO3 nighttime chemistry.

  13. THE GAS PHASE REACTION OF OZONE WITH 1,3-BUTADIENE: FORMATION YIELDS OF SOME TOXIC PRODUCTS. (R826236)

    EPA Science Inventory

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product yields. In separa...

  14. THE GAS PHASE REACTION OF OZONE WITH 1,3-BUTADIENE: FORMATION YIELDS OF SOME TOXIC PRODUCTS. (R826236)

    EPA Science Inventory

    The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product yields. In separa...

  15. Influence of galactic and solar cosmic rays on the Earth's atmosphere and atmosphere processes through nuclear and chemical reactions, and ionization; influence on formation of clouds and on atmospheric electrodynamics

    NASA Astrophysics Data System (ADS)

    Dorman, L. I.

    In this paper we continue our research described in the monograph 1 and consider the problem how CR influence on the atmosphere and atmosphere processes through nuclear reactions of primary and secondary CR with air and aerosol matter accompanied by the formation of many unstable and stable cosmogenic nuclides through the generation in the atmosphere of secondary relativistic electrons and EAS Extensive Atmospheric Showers playing a crucial role in atmospheric electric field phenomena through air ionization influences on the low ionosphere and radio wave propagation through induced chemical reactions influences on the chemistry of the atmosphere and the ozone layer as well as on the formation of clouds and influence on long-term global climate change section References 1 Lev I Dorman Cosmic Rays in the Earth s Atmosphere and Underground Kluwer Acad Publ Dordrecht Boston London 2004

  16. Review of heterogeneous photochemical reactions of NOy on aerosol - A possible daytime source of nitrous acid (HONO) in the atmosphere.

    PubMed

    Ma, Jinzhu; Liu, Yongchun; Han, Chong; Ma, Qingxin; Liu, Chang; He, Hong

    2013-02-01

    As an important precursor of hydroxyl radical, nitrous acid (HONO) plays a key role in the chemistry of the lower atmosphere. Recent atmospheric measurements and model calculations show strong enhancement for HONO formation during daytime, while they are inconsistent with the known sources in the atmosphere, suggesting that current models are lacking important sources for HONO. In this article, heterogeneous photochemical reactions of nitric acid/nitrate anion and nitrogen oxide on various aerosols were reviewed and their potential contribution to HONO formation was also discussed. It is demonstrated that HONO can be formed by photochemical reaction on surfaces with deposited HNO3, by photocatalytic reaction of NO2 on TiO2 or TiO2-containing materials, and by photochemical reaction of NO2 on soot, humic acids or other photosensitized organic surfaces. Although significant uncertainties still exist in the exact mechanisms and the yield of HONO, these additional sources might explain daytime observations in the atmosphere.

  17. Energy distribution among reaction products. VII - H + F2.

    NASA Technical Reports Server (NTRS)

    Polanyi, J. C.; Sloan, J. J.

    1972-01-01

    The 'arrested relaxation' variant of the IR chemiluminescence technique is used in a study of the distribution of vibrational, rotational and translational energies between the products of the reaction by which H + F2 yields HF + F. Diagrams are plotted and numerical values are obtained for the energy distribution rate constants.

  18. Ozone-cyclohexene reaction in air: quantitative analysis of particulate products and the reaction mechanism

    SciTech Connect

    Hatakeyama, S.; Tanonaka, T.; Weng, J.; Bandow, H.; Takagi, H.; Akimot, H.

    1985-10-01

    Both gaseous and particulate products of the cyclohexene-ozone reaction were analyzed. Major gaseous products were aldehydes that consist of adipaldehyde (CHO(CH/sub 2/)/sub 4/CHO), glutaraldehyde (CHO(CH/sub 2/)/sub 3/CHO), and pentanal (CH/sub 3/(CH/sub 2/)/sub 3/CHO). The sum of the primary yields of aldehydes reaches as high as 50%. In addition to aldehydes, formic acid, CO, and CO/sub 2/ were produced, but formaldehyde was not detected. Main particulate products were adipaldehyde, 6-oxohexanoic acid (CHO(CH/sub 2/)/sub 4/COOH), adipic acid (HOOC(CH/sub 2/)/sub 4/COOH), glutaraldehyde, 5-oxopentanoic acid (CHO(CH/sub 2/)/sub 3/COOH), and glutaric acid (HOOC(CH/sub 2/)/sub 3/COOH). All these compounds were analyzed quantitatively, and the fraction of initial cyclohexene converted to aerosol organic carbon was estimated to be 13 +/- 3% as the value extrapolated to a ppm concentration range of reactants. Although the reaction mechanism is in general explainable in terms of the Criegee mechanism, the reaction pathway to form formic acid is quite unique in this reaction system. The entire mechanism was discussed on the basis of the quantitative product analysis data.

  19. Products and kinetics of the heterogeneous reaction of particulate ametryn with NO3 radicals.

    PubMed

    Liu, Chang-Geng; Shu, Ji-Nian; Yang, Bo; Zhang, Peng

    2014-12-01

    As a renowned s-triazine herbicide, ametryn is worldwide emitted into the atmosphere in both gaseous and particulate phases via spray drifts from treatments and post application emissions, but its chemical degradation in the atmosphere has not been well characterized. In this study, the heterogeneous kinetics of particulate ametryn with NO3 radicals were investigated with a mixed-phase relative rate method. A vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and an atmospheric gas analysis mass spectrometer were synchronously used to online monitor the decays of particulate ametryn and gas-phase isoprene. The reactive uptake coefficient of NO3 radicals on ametryn particles was calculated to be 2.9 × 10(-2), according to the measured ametryn loss ratio and the average NO3 concentration. The effective rate constant for the heterogeneous reaction of particulate ametryn with NO3 radicals measured under experimental conditions was 8.4 × 10(-13) cm(3) molecule(-1) s(-1). In addition, atraton, ametryn sulfoxide and ametryn sulfone were identified as the reaction products by gas-chromatography-mass spectrometry (GC-MS) analysis. The experimental results might shed light on the chemical behavior of atmospheric ametryn at night-time.

  20. Atmospheric degradation of pyridine: UV absorption spectrum and reaction with OH radicals and O3

    NASA Astrophysics Data System (ADS)

    Errami, M.; El Dib, G.; Cazaunau, M.; Roth, E.; Salghi, R.; Mellouki, A.; Chakir, A.

    2016-10-01

    The UV absorption spectrum of pyridine and its gas phase reactions with OH radicals and O3 were investigated. UV absorption cross-sections were determined by using a D2-lamp system in the range 200-350 nm. The kinetic studies were carried out at room temperature and atmospheric pressure of purified air. The rate coefficient for the reaction of pyridine with OH was determined relative to that with acetone while that with O3 was measured under pseudo first order conditions. The rate coefficients obtained are (in cm3 molecule-1 s-1): k(OH + pyridine) = (5.40 ± 0.80) × 10-13 and k(O3 + pyridine) = (3.28 ± 1.70) × 10-20.

  1. Organic reactions increasing the absorption index of atmospheric sulfuric acid aerosols

    NASA Astrophysics Data System (ADS)

    Nozière, B.; Esteve, W.

    2005-02-01

    Unlike most environments present at Earth's surface atmospheric aerosols can be favorable to organic reactions. Among them, the acid-catalyzed aldol condensation of aldehydes and ketones produces light-absorbing compounds. In this work the increase of the absorption index of sulfuric acid solutions 50-96 wt. % resulting from the uptake of gas-phase acetaldehyde, acetone, and 2-butanone (methyl ethyl ketone), has been measured in the near UV and visible range. Our results indicate that the absorption index between 200 and 500 nm for stratospheric sulfuric aerosols exposed to 100 pptV of acetaldehyde (1 pptV = 10-12 v/v) would increase by four orders of magnitude over a two-year lifetime. Rough estimates based on previous radiative calculations suggest that this reaction could result in an increase of the radiative forcing of sulfate aerosols of the order of 0.01 W m-2, and that these processes are worth further investigation.

  2. Pion production in high-energy neutrino reactions with nuclei

    NASA Astrophysics Data System (ADS)

    Mosel, U.

    2015-06-01

    Background: A quantitative understanding of neutrino interactions with nuclei is needed for precision era neutrino long baseline experiments (MINOS, NOvA, DUNE) which all use nuclear targets. Pion production is the dominant reaction channel at the energies of these experiments. Purpose: Investigate the influence of nuclear effects on neutrino-induced pion production cross sections and compare predictions for pion-production with available data. Method: The Giessen Boltzmann-Uehling-Uhlenbeck (GiBUU) model is used for the description of all incoherent channels in neutrino-nucleus reactions. Results: Differential cross sections for charged and neutral pion production for the MINER ν A neutrino and antineutrino flux are calculated. An estimate for the coherent cross section is obtained from a comparison of data with theoretical results for incoherent cross sections. The invariant mass (W ) distribution of the Δ resonances produced is analyzed. Conclusions: Final state interactions affect the pion kinetic energy spectra significantly. The data for charged pion production at MINER ν A are compatible with the results of calculations using elementary data taken from an old Argonne National Laboratory experiment. Remaining differences for charged pion production can be attributed to coherent production; the data for antineutrino induced neutral pion production, where no coherent contribution is present, are reproduced quite well. The analysis of W distributions shows that sharp cuts on experimentally reconstructed invariant masses lead to shape distortions of the true W distributions for nuclear targets.

  3. Atmospheric photooxidation of alkylbenzenes—I. Carbonyl product analyses

    NASA Astrophysics Data System (ADS)

    Yu, Jianzhen; Jeffries, Harvey E.; Sexton, Kenneth G.

    Six alkylbenzenes—toluene, p-xylene, m-xylene, o-xylene, 1,3,5-trimethylbenzene and 1,2,4-trimethylbenzene—were selected to investigate the carbonyl products resulting from OH-initiated oxidation of aromatic compounds. Experiments were conducted in both indoor and outdoor smog chambers under simulated atmospheric conditions. Both batch samples and 30 min interval samples were taken in the outdoor smog chamber experiments using 1 ppmV alkylbenzene, 0.67 ppm NO x and sunlight as the light source. A wide variety of carbonyl products were detected and identified using gas chromatography/mass spectrometric (GC/MS) detection by their O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) derivatives. Among the observed carbonyl products are aromatic aldehydes, quinones, di-unsaturated 1,6-dicarbonyls, unsaturated 1,4-dicarbonyls, saturated dicarbonyls, hydroxy dicarbonyls, glycolaldehyde, hydroxy acetone, and possibly triones and epoxy carbonyls. Quantification was achieved using 13C 3-acetone as a gas-phase internal standard. The numerous carbonyl products detected in itself partially explain previous difficulties in balancing the reacted carbon. They also provide additional insight into the oxidation mechanism for aromatic compounds, which will be discussed in this paper.

  4. Methyl Chavicol: Characterization of its Biogenic Emission Rate, Abundance, and Oxidation Products in the Atmosphere

    NASA Astrophysics Data System (ADS)

    Bouvier-Brown, N. C.; Goldstein, A. H.; Worton, D. R.; Matross, D. M.; Gilman, J.; Kuster, W.; Degouw, J.; Cahill, T. M.; Holzinger, R.

    2008-12-01

    We report quantitative measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments: gas chromatograph with mass spectrometer detector (GC-MS), proton transfer reaction mass spectrometer (PTR-MS), and thermal desorption aerosol GC-MS (TAG). Previously identified as a potential bark beetle disruptant, methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO), a light and temperature dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4-68 % of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72-10.2 μ gCg-1h-1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many species. We propose this newly- characterized biogenic compound should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

  5. Hydrogen production from methane through catalytic partial oxidation reactions

    NASA Astrophysics Data System (ADS)

    Freni, S.; Calogero, G.; Cavallaro, S.

    This paper reviews recent developments in syn-gas production processes used for partial methane oxidation with and/or without steam. In particular, we examined different process charts (fixed bed, fluidised bed, membrane, etc.), kinds of catalysts (powders, foams, monoliths, etc.) and catalytically active phases (Ni, Pt, Rh, etc.). The explanation of the various suggested technical solutions accounted for the reaction mechanism that may selectively lead to calibrated mixtures of CO and H 2 or to the unwanted formation of products of total oxidation (CO 2 and H 2O) and pyrolysis (coke). Moreover, the new classes of catalysts allow the use of small reactors to treat large amounts of methane (monoliths) or separate hydrogen in situ from the other reaction products (membrane). This leads to higher conversions and selectivity than could have been expected thermodynamically. Although catalysts based on Rh are extremely expensive, they can be used to minimise H 2O formation by maximising H 2 yield.

  6. A study of the atmospherically important reactions between dimethyl selenide (DMSe) and molecular halogens (X2 = Cl2, Br2, and I2) with ab initio calculations.

    PubMed

    Rhyman, Lydia; Armata, Nerina; Ramasami, Ponnadurai; Dyke, John M

    2012-06-14

    The atmospherically relevant reactions between dimethyl selenide (DMSe) and the molecular halogens (X(2) = Cl(2), Br(2), and I(2)) have been studied with ab initio calculations at the MP2/aug-cc-pVDZ level of theory. Geometry optimization calculations showed that the reactions proceed from the reagents to the products (CH(3)SeCH(2)X + HX) via three minima, a van der Waals adduct (DMSe:X(2)), a covalently bound intermediate (DMSeX(2)), and a product-like complex (CH(3)SeCH(2)X:HX). The computed potential energy surfaces are used to predict what molecular species are likely to be observed in spectroscopic experiments such as gas-phase photoelectron spectroscopy and infrared matrix isolation spectroscopy. It is concluded that, for the reactions of DMSe with Cl(2) and Br(2), the covalent intermediate should be seen in spectroscopic experiments, whereas, in the DMSe + I(2) reaction, the van der Waals adduct DMSe:I(2) should be observed. Comparison is made with previous related calculations and experiments on dimethyl sulfide (DMS) with molecular halogens. The relevance of the results to atmospheric chemistry is discussed. The DMSeX(2) and DMSe:X(2) intermediates are likely to be reservoirs of molecular halogens in the atmosphere which will lead on photolysis to ozone depletion.

  7. Molecular activation by surface coordination model: Insight into heterogeneous atmospheric chemistry through cluster-ion molecule reactions

    NASA Astrophysics Data System (ADS)

    Mactaylor, Ronald T. Stanford

    One specific discipline for which cluster work has particular relevance is atmospheric science. The original application of the fast flow reactor technique employed in this thesis was atmospheric science. Coincidentally, fast flow reactors are readily adaptable to cluster studies and in some cases the optimal methodology. Successive studies of a chemical reaction over a range of pressures using a fast flow reactor can allow the experimentalist to distinguish whether a reaction product is formed by a bimolecular or termolecular mechanism. This type of study applied to the HCl water cluster system revealed two distinct processes for HCl uptake. The bimolecular and termolecular HCl uptake processes, noted along with the specific ratios of water molecules to HCl molecules lead directly to the Molecular Activation by Surface Coordination model for heterogeneous processes involving HCl on water-ice polar stratospheric clouds. The efficiency of the termolecular uptake process indicated a strong interaction with the cluster. Since the association product is only observable on clusters where one HCl has already been incorporated by a bimolecular process, and this bimolecular process is interpreted as ionic dissolution, the logical conclusion is that the efficient association process must involve an ion-induced dipole interaction. The ramifications of this conclusion are that it is possible that the efficient heterogeneous chemical conversion processes which are required to explain polar stratospheric ozone loss, are in part due to the surface coordination of HCl (making it readily available to participate in reactions) and also a chemical activation aspect resulting from an ion-induced dipole. A noteworthy feature of this model is that it ties together the results of many studies of the HCl/ice system, which previously did not appear to be in accord with one another. Further exploration of the HCl protonated water cluster system reveal striking similarities to surface

  8. Sorption enhanced reaction process (SERP) for production of hydrogen

    SciTech Connect

    Sircar, S.; Anand, M.; Carvill, B.

    1995-09-01

    Sorption Enhanced Reaction (SER) is a novel process that is being developed for the production of lower cost hydrogen by steam-methane reforming (SMR). In this process, the reaction of methane with steam is carried out in the presence of an admixture of a catalyst and a selective adsorbent for carbon dioxide. The consequences of SER are: (1) reformation reaction at a significantly lower temperature (300-500{degrees}C) than conventional SMR (800-1100{degrees}C), while achieving the same conversion of methane to hydrogen, (2) the product hydrogen is obtained at reactor pressure (200-400 psig) and at 99+% purity directly from the reactor (compared to only 70-75% H{sub 2} from conventional SMR reactor), (3) downstream hydrogen purification step is either eliminated or significantly reduced in size. The early focus of the program will be on the identification of an adsorbent/chemisorbent for CO{sub 2} and on the demonstration of the SER concept for SMR in our state-of-the-art bench scale process. In the latter stages, a pilot plant will be built to scale-up the technology and to develop engineering data. The program has just been initiated and no significant results for SMR will be reported. However, results demonstrating the basic principles and process schemes of SER technology will be presented for reverse water gas shift reaction as the model reaction. If successful, this technology will be commercialized by Air Products and Chemicals, Inc. (APCI) and used in its existing hydrogen business. APCI is the world leader in merchant hydrogen production for a wide range of industrial applications.

  9. Ion/molecule reaction and ion evaporation in atmospheric pressure spray ionization

    NASA Astrophysics Data System (ADS)

    Hirabayashi, Atsumu; Takada, Yasuaki; Kambara, Hideki; Umemura, Yuta; Ohta, Hitoshi; Ito, Haruhiko; Kuchitsu, Kozo

    1992-12-01

    The positive ions produced in atmospheric pressure spray ionization of ammonia, alanine and sucrose in aqueous solution were detected with a double-focusing mass spectrometer. The relative intensities of the quasi-molecular ions of ammonia, NH+4 (H2O)n (n = 0-3), were found to be proportional to the concentration of the ammonia solution and to increase with increasing distance d between the nozzle tip and the sample aperture of the mass spectrometer; this observation shows that the ammonia molecule is produced by the spray and is protonated at atmospheric pressure by a proton transfer reaction with the hydronium ion and its hydrated clusters. The observed dependences of the relative intensities of the protonated alanine molecules from alanine solution and the cationized sucrose molecules from sucrose solution on d show that some part of these quasi-molecular ions are also produced by the ion/molecule reaction in the gas phase. However, their dependences on the concentration, which are steeper than that in the ammonia case, indicate that a significant proportion of these ions are produced by ion evaporation from a droplet or liquid.

  10. VIIRS Atmospheric Products in the Community Satellite Processing Package (CSPP)

    NASA Astrophysics Data System (ADS)

    Cureton, G. P.; Gumley, L.; Mindock, S.; Martin, G.; Garcia, R. K.; Strabala, K.

    2012-12-01

    The Cooperative Institute for Meteorological Satellite Studies (CIMSS) has a long history of supporting the Direct Broadcast (DB) community for various sensors, recently with the International MODIS/AIRS Processing Package (IMAPP) for the NASA EOS polar orbiters Terra and Aqua. CIMSS has continued this effort into the NPP/JPSS (previously NPOESS) era with the development of the Community Satellite Processing Package (CSPP), supporting the VIIRS, CrIS and ATMS sensors on the Suomi National Polar-orbiting Partnership (Suomi NPP) spacecraft. In time it is intended that CSPP will support GOES-R, JPSS and other geostationary and polar orbiting platforms. Here we focus on the implementation and usage of the Visible Infrared Imaging Radiometer Suite (VIIRS) atmospheric product sub-packages within CSPP, which are based on the Interface Data Processing Segment (IDPS) code as implemented by Raytheon in the Algorithm Development Library (ADL). The VIIRS atmospheric algorithms available in CSPP include the Cloud Mask, Active Fires, Cloud Optical Properties, Cloud Top Parameters, and the Aerosol Optical Thickness algorithms. Each ADL sub-package consists of a binary executable and a series of configuration XML files. A series of python scripts handle ancillary data retrieval and preparation for ingest into ADL, manage algorithm execution, and provide a variety of execution options which are of utility in operational and algorithm development settings. Examples of these options, applied to operational and direct-broadcast VIIRS SDR data, are described.

  11. The Atmospheric Infrared Sounder Version 6 Cloud Products

    NASA Technical Reports Server (NTRS)

    Kahn, B. H.; Irion, F. W.; Dang, V. T.; Manning, E. M.; Nasiri, S. L.; Naud, C. M.; Blaisdell, J. M.; Schreier, M. M..; Yue, Q.; Bowman, K. W.; hide

    2014-01-01

    The version 6 cloud products of the Atmospheric Infrared Sounder (AIRS) and Advanced Microwave Sounding Unit (AMSU) instrument suite are described. The cloud top temperature, pressure, and height and effective cloud fraction are now reported at the AIRS field-of-view (FOV) resolution. Significant improvements in cloud height assignment over version 5 are shown with FOV-scale comparisons to cloud vertical structure observed by the CloudSat 94 GHz radar and the Cloud-Aerosol LIdar with Orthogonal Polarization (CALIOP). Cloud thermodynamic phase (ice, liquid, and unknown phase), ice cloud effective diameter D(sub e), and ice cloud optical thickness (t) are derived using an optimal estimation methodology for AIRS FOVs, and global distributions for 2007 are presented. The largest values of tau are found in the storm tracks and near convection in the tropics, while D(sub e) is largest on the equatorial side of the midlatitude storm tracks in both hemispheres, and lowest in tropical thin cirrus and the winter polar atmosphere. Over the Maritime Continent the diurnal variability of tau is significantly larger than for the total cloud fraction, ice cloud frequency, and D(sub e), and is anchored to the island archipelago morphology. Important differences are described between northern and southern hemispheric midlatitude cyclones using storm center composites. The infrared-based cloud retrievals of AIRS provide unique, decadal-scale and global observations of clouds over portions of the diurnal and annual cycles, and capture variability within the mesoscale and synoptic scales at all latitudes.

  12. Glow-Discharge Production of Oxygen from the Martian Atmosphere

    NASA Astrophysics Data System (ADS)

    Hughes, Caleb; Outlaw, Ronald

    One of the most crucial aspects of any mission to Mars is a continual supply of oxygen for astronaut respiration on site. The most popular approach to this problem favors in-situ oxygen production on Mars, utilizing the CO2 Martian atmosphere. However, this requires a large energy budget. NASA's current plans for Mars include sending a system called MOXIE, which produces oxygen through solid oxide electrolysis at high temperatures. An alternative approach utilizes the 6 Torr Martian atmosphere to provide a continual source of oxygen by breaking down the molecule into CO and O using a glow-discharge. After dissociation, a thin film Agmembrane uniquely permeates the atomic oxygen which then recombines to O2 on the downstream side, where it is subsequently stored. By taking advantage of recent advances in thin film technology to reduce the thickness of the film to many orders of magnitude less than used in the initial study, a corresponding increase in O2 flux can be realized. The Ag thin film requires the support of a porous ceramic substructure. With this system, it is shown that this method produces a viable energy efficient alternative to MOXIE.

  13. An impact-induced terrestrial atmosphere and iron-water reactions during accretion of the Earth

    NASA Technical Reports Server (NTRS)

    Lange, M. A.; Ahrens, T. J.

    1985-01-01

    Shock wave data and theoretical calculations were used to derive models of an impact-generated terrestrial atmosphere during accretion of the Earth. The models showed that impacts of infalling planetesimals not only provided the entire budget of terrestrial water but also led to a continuous depletion of near-surface layers of water-bearing minerals of their structural water. This resulted in a final atmospheric water reservoir comparable to the present day total water budget of the Earth. The interaction of metallic iron with free water at the surface of the accreting Earth is considered. We carried out model calcualtions simulating these processes during accretion. It is assumed that these processes are the prime source of the terrestrial FeO component of silicates and oxides. It is demonstrated that the iron-water reaction would result in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed. In order to obtain the necessary amount of terrestrial water, slightly heterogeneous accretion with initially 36 wt% iron planetesimals, as compared with a homogeneous value of 34 wt% is required.

  14. Kinetics of suprathermal hydrogen atom reactions with saturated hydrides in planetary and satellite atmospheres

    NASA Astrophysics Data System (ADS)

    Morton, Richard J.; Kaiser, Ralf I.

    2003-05-01

    The kinetics of saturated hydrides methane (CH 4), silane (SiH 4), germane (GeH 4), ammonia (NH 3), phosphine (PH 3), arsane (AsH 3), water (H 2O), and hydrogen sulfide (H 2S) in the low-temperature atmospheres of Jupiter, Saturn, Uranus, Neptune, Pluto, Titan, and Triton reacting with suprathermal hydrogen atoms were investigated computationally to extract suprathermal rate constants k( E) via an inverse Laplace transformation from experimentally available thermal rate constants k( T). Our data reveal that all suprathermal rate constants range up to 10 -10 cm3 s-1, whereas the thermal counterparts are as low as 8×10 -73 cm3 s-1. These data demonstrate explicitly a significantly enhanced reactivity of photolytically generated suprathermal hydrogen atoms in the low-temperature planetary and satellite atmospheres and suggest that this hitherto unaccounted reaction class should be included by the planetary modeling community into future photochemical networks of atmospheres of outer solar system planets and their moons.

  15. An impact-induced terrestrial atmosphere and iron-water reactions during accretion of the Earth

    NASA Technical Reports Server (NTRS)

    Lange, M. A.; Ahrens, T. J.

    1985-01-01

    Shock wave data and theoretical calculations were used to derive models of an impact-generated terrestrial atmosphere during accretion of the Earth. The models showed that impacts of infalling planetesimals not only provided the entire budget of terrestrial water but also led to a continuous depletion of near-surface layers of water-bearing minerals of their structural water. This resulted in a final atmospheric water reservoir comparable to the present day total water budget of the Earth. The interaction of metallic iron with free water at the surface of the accreting Earth is considered. We carried out model calcualtions simulating these processes during accretion. It is assumed that these processes are the prime source of the terrestrial FeO component of silicates and oxides. It is demonstrated that the iron-water reaction would result in the absence of atmospheric/hydrospheric water, if homogeneous accretion is assumed. In order to obtain the necessary amount of terrestrial water, slightly heterogeneous accretion with initially 36 wt% iron planetesimals, as compared with a homogeneous value of 34 wt% is required.

  16. Investigation of the Photochemistry in Saturn's Ring Shadowed Atmosphere: Production Rates of Key Atmospheric Molecules

    NASA Astrophysics Data System (ADS)

    Edgington, S. G.; Atreya, S. K.; Wilson, E. H.; Baines, K. H.; West, R. A.; Bjoraker, G. L.; Fletcher, L.

    2011-12-01

    Cassini has been orbiting Saturn for well over seven years. During this epoch, the ring shadow has changed from shading a large portion of the northern hemisphere to shading a small region just south of the equator and is continuing southward. At Saturn Orbit Insertion (July 1, 2004), the ring plane was inclined by ~24 degrees relative to the Sun-Saturn vector. The projection of the B-ring onto Saturn reached as far as 40N along the central meridian (~52N at the terminator). At its maximum extent, the ring shadow can reach as far as 48N (~58N at the terminator). The net result, is that the intensity of both ultraviolet and visible sunlight penetrating into any particular northern/southern latitude will vary depending on Saturn's tilt relative to the Sun and the optical thickness of each ring system. Previous work [1] looked at the variation of the solar flux as a function of solar inclination, i.e. season (see Figure 1). The current work looks at the impact of the oscillating ring shadow on the photodissociation and production rates of key molecules in Saturn's stratosphere and upper troposphere over time. Beginning with methane, the impact on production and loss rates of the long-lived photochemical hydrocarbons leading to haze formation are examined at several latitudes over a Saturn year. We also look at the impacts on phosphine abundance, a disequilibrium species whose presence in the upper troposphere is a tracer of convection processes in the deep atmosphere. Comparison to the corresponding photodissociation rates for a clear atmosphere and the effect of dynamical mixing will be presented. [1] Edgington,S.G., et al., 2006. Adaptation of a 2-D Photochemical Model to Improve Our Understanding of Saturn's Atmosphere. B.A.A.S., 38, 499 (#11.23). The research described in this paper was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration.

  17. A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan.

    PubMed

    Zymak, Illia; Žabka, Ján; Polášek, Miroslav; Španěl, Patrik; Smith, David

    2016-11-01

    Reliable theoretical models of the chemical kinetics of the ionosphere of Saturn's moon, Titan, is highly dependent on the precision of the rates of the reactions of ambient ions with hydrocarbon molecules at relevant temperatures. A Variable Temperature Selected Ions Flow Tube technique, which has been developed primarily to study these reactions at temperatures within the range of 200-330 K, is briefly described. The flow tube temperature regulation system and the thermalisation of ions are also discussed. Preliminary studies of two reactions have been carried out to check the reliability and efficacy of kinetics measurements: (i) Rate constants of the reaction of CH3(+) ions with molecular oxygen were measured at different temperatures, which indicate values in agreement with previous ion cyclotron resonance measurements ostensibly made at 300 K. (ii) Formation of CH3(+) ions in the reaction of N2(+) ions with CH4 molecules were studied at temperatures within the range 240-310 K which showed a small but statistically significant decrease of the ratio of product CH3(+) ions to reactant N2(+) ions with reaction temperature.

  18. Yields of O2(b 1 Sigma g +) from reactions of HO2. [in planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Keyser, L. F.; Choo, K. Y.; Leu, M. T.

    1985-01-01

    The production of O2(b 1 Sigma g +) has been monitored for several reactions of the HO2 radical at 300 K using a discharge-flow apparatus with resonance fluorescence and chemiluminescence detection. In all cases, the resulting quantum efficiencies were found to be less than 0.03. O2(b) was observed when F atoms were added to H2O2 in the gas phase. The signal strengths of O2(b) were proportional to initial concentrations of HO2 formed by the F + H2O2 reaction. Observed /O2(b)/, /HO2/, and /OH/ vs /F/0 were analyzed using a simple three-step mechanism and a more complete computer simulation with 22 reaction steps. The results indicate that the F + HO2 reaction yields O2(b) with an efficiency of (3.6 + or - 1.4) x 10 to the -3rd. Yields from the O + OH2 reaction were less than 0.02, indicating that this reaction cannot be a major source of the O2(b) emission observed in the earth's nightglow.

  19. A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan

    NASA Astrophysics Data System (ADS)

    Zymak, Illia; Žabka, Ján; Polášek, Miroslav; Španěl, Patrik; Smith, David

    2016-11-01

    Reliable theoretical models of the chemical kinetics of the ionosphere of Saturn's moon, Titan, is highly dependent on the precision of the rates of the reactions of ambient ions with hydrocarbon molecules at relevant temperatures. A Variable Temperature Selected Ions Flow Tube technique, which has been developed primarily to study these reactions at temperatures within the range of 200-330 K, is briefly described. The flow tube temperature regulation system and the thermalisation of ions are also discussed. Preliminary studies of two reactions have been carried out to check the reliability and efficacy of kinetics measurements: (i) Rate constants of the reaction of CH3 + ions with molecular oxygen were measured at different temperatures, which indicate values in agreement with previous ion cyclotron resonance measurements ostensibly made at 300 K. (ii) Formation of CH3 + ions in the reaction of N2 + ions with CH4 molecules were studied at temperatures within the range 240-310 K which showed a small but statistically significant decrease of the ratio of product CH3 + ions to reactant N2 + ions with reaction temperature.

  20. Changes in atmospheric composition inferred from ionospheric production rates

    NASA Technical Reports Server (NTRS)

    Titheridge, J. E.

    1974-01-01

    Changes in the total electron content of the ionosphere near sunrise are used to determine the integrated production rate in the ionosphere (Q) from 1965 to 1971 at latitudes of 34S, 20N, and 34N. The observed regular semiannual variation in Q through a range of 1:3:1 is interpreted as an increase in the ratio O/N2 (relative densities) near the equinoxes. It follows that there is a worldwide semiannual variation in atmospheric composition, with the above ratio maximum just after the equinoxes. There is a large seasonal variation in the Northern hemisphere with a maximum in mid-summer. This effect is absent in the Southern hemisphere. At all times except solar maximum in the Northern hemisphere there is a global asymmetry. The ratio O/N2 is about three times as large in the Northern hemisphere. The overall mechanism appears to be N2 absorption.

  1. A SIFT ion-molecule study of some reactions in Titan's atmosphere. reactions of N(+), N(2)(+), and HCN(+) with CH(4), C(2)H(2), and C(2)H(4)

    NASA Technical Reports Server (NTRS)

    Anicich, Vincent G.; Wilson, Paul; McEwan, Murray J.

    2004-01-01

    The results of a study of the ion-molecule reactions of N(+), N(2)(+), and HCN(+) with methane, acetylene, and ethylene are reported. These studies were performed using the FA-SIFT at the University of Canterbury. The reactions studied here are important to understanding the ion chemistry in Titan's atmosphere. N(+) and N(2)(+) are the primary ions formed by photo-ionization and electron impact in Titan's ionosphere and drive Titan's ion chemistry. It is therefore very important to know how these ions react with the principal trace neutral species in Titan's atmosphere: Methane, acetylene, and ethylene. While these reactions have been studied before the product channels have been difficult to define as several potential isobaric products make a definitive answer difficult. Mass overlap causes difficulties in making unambiguous species assignments in these systems. Two discriminators have been used in this study to resolve the mass overlap problem. They are deuterium labeling and also the differences in reactivities of each isobar with various neutral reactants. Several differences have been found from the products in previous work. The HCN(+) ion is important in both Titan's atmosphere and in the laboratory.

  2. A SIFT ion-molecule study of some reactions in Titan's atmosphere. reactions of N(+), N(2)(+), and HCN(+) with CH(4), C(2)H(2), and C(2)H(4).

    PubMed

    Anicich, Vincent G; Wilson, Paul; McEwan, Murray J

    2004-08-01

    The results of a study of the ion-molecule reactions of N(+), N(2)(+), and HCN(+) with methane, acetylene, and ethylene are reported. These studies were performed using the FA-SIFT at the University of Canterbury. The reactions studied here are important to understanding the ion chemistry in Titan's atmosphere. N(+) and N(2)(+) are the primary ions formed by photo-ionization and electron impact in Titan's ionosphere and drive Titan's ion chemistry. It is therefore very important to know how these ions react with the principal trace neutral species in Titan's atmosphere: Methane, acetylene, and ethylene. While these reactions have been studied before the product channels have been difficult to define as several potential isobaric products make a definitive answer difficult. Mass overlap causes difficulties in making unambiguous species assignments in these systems. Two discriminators have been used in this study to resolve the mass overlap problem. They are deuterium labeling and also the differences in reactivities of each isobar with various neutral reactants. Several differences have been found from the products in previous work. The HCN(+) ion is important in both Titan's atmosphere and in the laboratory.

  3. A SIFT ion-molecule study of some reactions in Titan's atmosphere. reactions of N(+), N(2)(+), and HCN(+) with CH(4), C(2)H(2), and C(2)H(4)

    NASA Technical Reports Server (NTRS)

    Anicich, Vincent G.; Wilson, Paul; McEwan, Murray J.

    2004-01-01

    The results of a study of the ion-molecule reactions of N(+), N(2)(+), and HCN(+) with methane, acetylene, and ethylene are reported. These studies were performed using the FA-SIFT at the University of Canterbury. The reactions studied here are important to understanding the ion chemistry in Titan's atmosphere. N(+) and N(2)(+) are the primary ions formed by photo-ionization and electron impact in Titan's ionosphere and drive Titan's ion chemistry. It is therefore very important to know how these ions react with the principal trace neutral species in Titan's atmosphere: Methane, acetylene, and ethylene. While these reactions have been studied before the product channels have been difficult to define as several potential isobaric products make a definitive answer difficult. Mass overlap causes difficulties in making unambiguous species assignments in these systems. Two discriminators have been used in this study to resolve the mass overlap problem. They are deuterium labeling and also the differences in reactivities of each isobar with various neutral reactants. Several differences have been found from the products in previous work. The HCN(+) ion is important in both Titan's atmosphere and in the laboratory.

  4. Maillard reaction products from chitosan-xylan ionic liquid solution.

    PubMed

    Luo, Yuqiong; Ling, Yunzhi; Wang, Xiaoying; Han, Yang; Zeng, Xianjie; Sun, Runcang

    2013-10-15

    A facile method is reported to prepare Maillard reaction products (MRPs) from chitosan and xylan in co-solvent ionic liquid. UV absorbance and fluorescence changes were regarded as indicators of the occurrence of Maillard reaction. FT-IR, NMR, XRD and TG were used to investigate the structure of chitosan-xylan conjugate. The results revealed that when chitosan reacted with xylan in ionic liquid, the hydrogen bonds in chitosan were destroyed, the facts resulted in the formation of chitosan-xylan MRPs. Moreover, when the mass ratio of chitosan to xylan was 1:1, the Maillard reaction proceeded easily. In addition, relatively high antioxidant property was also noted for the chitosan-xylan conjugate with mass ratio 1:1. So the obtained chitosan-xylan MRP is a promising antioxidant agent for food industry. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Taste-active maillard reaction products: the "tasty" world of nonvolatile maillard reaction products.

    PubMed

    Hofmann, Thomas

    2005-06-01

    This study was done to obtain greater insight into the structures and sensory activities of those tastants that are not present in foods per se, but are generated during food processing by Maillard-type reactions from carbohydrates and amino acids and thus remain unknown. In order to rank the tastants according to their relative taste impact and to identify the key tastants generated during thermal food processing, the so-called taste dilution analysis (TDA), which uses the human tongue as a biosensor for tastants, was applied to heated, intensely bitter tasting binary mixtures of glucose or xylose and proline or alanine, respectively. This screening technique led to the identification of previously unknown taste compounds, among which intensely bitter tastants such as quinizolate and homoquinizolate, a pungent-tasting pyranopyranone, cyclopentenone derivatives exhibiting a physiological cooling effect, as well as a taste-enhancing pyridinium betaine named alapyridaine will be presented.

  6. A survey of bimolecular ion-molecule reactions for use in modeling the chemistry of planetary atmospheres, cometary comae, and interstellar clouds - 1993 supplement

    NASA Technical Reports Server (NTRS)

    Anicich, V. G.

    1993-01-01

    This is a supplement to a previous paper (Anicich & Huntress 1986). It is a survey of bimolecular positive ion-molecule reactions with potential importance to the chemistry of planetary atmospheres, cometary comae, and interstellar clouds. This supplement covers the literature from 1986 through 1991, with some additional citations missed in the original survey. Over 200 new citations are included. A table of reactions is listed by reactant ion, and cross-references are provided for both ionic and neutral reactants and also for both ionic and neutral products.

  7. A survey of bimolecular ion-molecule reactions for use in modeling the chemistry of planetary atmospheres, cometary comae, and interstellar clouds - 1993 supplement

    NASA Technical Reports Server (NTRS)

    Anicich, V. G.

    1993-01-01

    This is a supplement to a previous paper (Anicich & Huntress 1986). It is a survey of bimolecular positive ion-molecule reactions with potential importance to the chemistry of planetary atmospheres, cometary comae, and interstellar clouds. This supplement covers the literature from 1986 through 1991, with some additional citations missed in the original survey. Over 200 new citations are included. A table of reactions is listed by reactant ion, and cross-references are provided for both ionic and neutral reactants and also for both ionic and neutral products.

  8. FTIR product distribution study of the Cl and OH initiated degradation of methyl acrylate at atmospheric pressure.

    PubMed

    Blanco, María B; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A

    2010-09-15

    A product study is reported on the gas-phase reactions of OH radicals and Cl atoms with methyl acrylate. The experiments were performed in a 1080-L quartz-glass chamber in synthetic air at 298 ± 2 K and 760 ± 10 Torr using long-path in situ FTIR spectroscopy for the analysis of the reactants and products. In the absence of NO(x) the major product observed in the OH reaction is methyl glyoxylate, with formaldehyde as a coproduct. For the reaction with Cl only formyl chloride (HC(O)Cl), CO, and HCl could be positively identified as products, however, the concentration-time behavior of these products show that they are secondary products and originate from the further oxidation of a major primary product. From this behavior and a comparison with simulated spectra unidentified bands in the residual product spectra are tentatively attributed to a compound of structure CH(2)ClC(O)C(O)OCH(3), i.e., formation of methyl 3-chloro-2-oxopropanoate from the reaction of Cl with methyl acrylate. The present results are compared with previous results where available and simple atmospheric degradation mechanisms are postulated to explain the formation of the observed products.

  9. Dual Position Sensitive MWPC for tracking reaction products at VAMOS++

    NASA Astrophysics Data System (ADS)

    Vandebrouck, M.; Lemasson, A.; Rejmund, M.; Fremont, G.; Pancin, J.; Navin, A.; Michelagnoli, C.; Goupil, J.; Spitaels, C.; Jacquot, B.

    2016-03-01

    The characteristics and performance of a Dual Position Sensitive Multi-Wire Proportional Counter (DPS-MWPC) used to measure the scattering angle, the interaction position on the target and the velocity of reaction products detected in the VAMOS++ magnetic spectrometer, are reported. The detector consists of a pair of position sensitive low pressure MWPCs and provides both fast timing signals, along with the two-dimensional position coordinates required to define the trajectory of the reaction products. A time-of-flight resolution of 305(11) ps (FWHM) was measured. The measured resolutions (FWHM) were 2.5(3) mrad and 560(70) μm for the scattering angle and the interaction point at the target respectively. The subsequent improvement of the Doppler correction of the energy of the γ-rays, detected in the γ-ray tracking array AGATA in coincidence with isotopically identified ions in VAMOS++, is also discussed.

  10. Product detection of the CH radical reaction with acetaldehyde.

    PubMed

    Goulay, Fabien; Trevitt, Adam J; Savee, John D; Bouwman, Jordy; Osborn, David L; Taatjes, Craig A; Wilson, Kevin R; Leone, Stephen R

    2012-06-21

    The reaction of the methylidyne radical (CH) with acetaldehyde (CH(3)CHO) is studied at room temperature and at a pressure of 4 Torr (533.3 Pa) using a multiplexed photoionization mass spectrometer coupled to the tunable vacuum ultraviolet synchrotron radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory. The CH radicals are generated by 248 nm multiphoton photolysis of CHBr(3) and react with acetaldehyde in an excess of helium and nitrogen gas flow. Five reaction exit channels are observed corresponding to elimination of methylene (CH(2)), elimination of a formyl radical (HCO), elimination of carbon monoxide (CO), elimination of a methyl radical (CH(3)), and elimination of a hydrogen atom. Analysis of the photoionization yields versus photon energy for the reaction of CH and CD radicals with acetaldehyde and CH radical with partially deuterated acetaldehyde (CD(3)CHO) provides fine details about the reaction mechanism. The CH(2) elimination channel is found to preferentially form the acetyl radical by removal of the aldehydic hydrogen. The insertion of the CH radical into a C-H bond of the methyl group of acetaldehyde is likely to lead to a C(3)H(5)O reaction intermediate that can isomerize by β-hydrogen transfer of the aldehydic hydrogen atom and dissociate to form acrolein + H or ketene + CH(3), which are observed directly. Cycloaddition of the radical onto the carbonyl group is likely to lead to the formation of the observed products, methylketene, methyleneoxirane, and acrolein.

  11. Polysorbate 80 in medical products and nonimmunologic anaphylactoid reactions.

    PubMed

    Coors, Esther A; Seybold, Heidi; Merk, Hans F; Mahler, Vera

    2005-12-01

    Polyoxyethylene-sorbitan-20-monooleate (also known as polysorbate 80 and Tween 80) is a solubilizing agent ubiquitously used in nutritives, creams, ointments, lotions, and multiple medical preparations (e.g., vitamin oils, vaccines, and anticancer agents) and as an additive in tablets. Whereas its relevance as a contact allergen has declined during the past decades, it is of current relevance as a "hidden" inductor of anaphylactoid reactions. To identify polysorbate 80 (generally believed to be an inert vehicle) as an inductor of a severe anaphylactoid reaction. Skin prick testing, enzyme-linked immunosorbent assay, IgE immunoblotting, and flow cytometric detection of basophil activation were performed in controls and in a patient with a medical history of anaphylactic shock due to intravenous administration of a multivitamin product during pregnancy. Polysorbate 80 was identified as the causative agent for the anaphylactoid reaction of nonimmunologic origin in the patient. Polysorbate specific IgE antibodies were not identified in enzyme-linked immunosorbent assay and immunoblot examinations, confirming the nonimmunologic nature of the anaphylactoid reaction. Polysorbate 80 is a ubiquitously used solubilizing agent that can cause severe nonimmunologic anaphylactoid reactions.

  12. Liquid-phase reactions induced by atmospheric pressure glow discharge with liquid electrode

    NASA Astrophysics Data System (ADS)

    Tochikubo, Fumiyoshi; Shirai, Naoki; Uchida, Satoshi

    2014-12-01

    We experimentally investigated some of the initial reactions in a liquid induced by electron or positive-ion irradiation from an atmospheric-pressure dc glow discharge in contact with the liquid. We used an H-shaped glass reactor to observe the effects of electron irradiation and positive-ion irradiation on the liquid-phase reaction separately and simultaneously. Aqueous solutions of NaCl, AgNO3, HAuCl4, and FeCl2 are used as the electrolyte. Solutions of AgNO3 and HAuCl4 are used for the generation of Ag and Au nanoparticles, respectively. Solution of FeCl2 is used for the generation of ferromagnetic particles. Experimental results showed that electron irradiation of the liquid surface generates OH- in water and that positive-ion irradiation of the liquid surface generates H+ in water even without the dissolution of gas-phase nitrogen oxide. A possible reaction process is qualitatively discussed. We also showed that the control of reductive and oxidative environment in the liquid is possible not only by the gas composition for the plasma generation but also by the liquid composition.

  13. Multiresolution wavelet-based simulation of transport and photochemical reactions in the atmosphere

    NASA Astrophysics Data System (ADS)

    Heidarinasab, Amir; Dabir, Bahram; Sahimi, Muhammad

    We propose a novel approach for coarsening of computational grids that are used in the modelling of air pollution problems and climate change phenomena at large length scales. The method is based on the use of wavelet transformations. Starting with a fine-scale computational grid, the resolution of which depends on the amount of the experimental data that are available, as well as the topography of the area under study, a wavelet transformation is used to systematically coarsen the grid in those zones in which the fine details of the grid are not necessary, while preserving all the important information and the grid resolution in those regions where large-scale variations in the properties of interest occur. The coarsening can be static and fixed, based on the topography alone, or can be dynamic so as to produce a grid structure that varies with the time. We show that the computations for modelling transport and photochemical reactions (and the associated air pollution problems) with the new approach are orders of magnitude more efficient than the most efficient method currently available, and may render unnecessary use of massively parallel or vectorized computational strategies. To demonstrate the efficiency of the method, we study transport and photochemical reactions of 51 species, involving 117 nonlinear reactions, in the atmosphere of Tehran, Iran, a large urban area with severe air pollution problems.

  14. Common inorganic ions are efficient catalysts for organic reactions in atmospheric aerosols and other natural environments

    NASA Astrophysics Data System (ADS)

    Nozière, B.; Dziedzic, P.; Córdova, A.

    2009-01-01

    In this work, inorganic ammonium ions, NH4+, and carbonate ions, CO32-, are reported for the first time as catalysts for organic reactions in atmospheric aerosols and other natural environments at the Earth's surface. These reactions include the formation of C-C and C-O bonds by aldol condensation and acetal formation, and reveal a new aspect of the interactions between organic and inorganic materials in natural environments. The catalytic properties of inorganic ammonium ions, in particular, were not previously known in chemistry. The reactions were found to be as fast in tropospheric ammonium sulfate composition as in concentrated sulfuric acid. The ubiquitous presence and large concentrations of ammonium ions in tropospheric aerosols would make of ammonium catalysis a main consumption pathway for organic compounds in these aerosols, while acid catalysis would have a minor contribution. In particular, ammonium catalysis would account quantitatively for the aging of carbonyl compounds into secondary ''fulvic'' compounds in tropospheric aerosols, a transformation affecting the optical properties of these aerosols. In general, ammonium catalysis is likely to be responsible for many observations previously attributed to acid catalysis in the troposphere.

  15. In situ measurements of heterogeneous reactions on ambient aerosol particles: Impacts on atmospheric chemistry and climate

    SciTech Connect

    Bertram, Timothy

    2015-02-11

    Aerosol particles play a critical role in the Earth’s energy budget through the absorption and scattering of radiation, and/or through their ability to form clouds and alter cloud lifetime. Heterogeneous and multi-phase reactions alter the climate-relevant properties of aerosol particles and catalyze reaction pathways that are energetically unfavorable in the gas phase. The chemical composition of aerosol particles dictates the kinetics of heterogeneous and multi-phase reactions. At present, the vast majority of the molecular level information on these processes has been determined in laboratory investigations on model aerosol systems. The work described here provides a comprehensive investigation into the reactivity of complex, ambient aerosol particles is proposed to determine: 1) how representative laboratory investigations of heterogeneous and multi-phase processes conducted on model, simple systems are of the real atmosphere, and 2) the impact of heterogeneous and multi-phase processes on ambient particle optical properties and their ability to nucleate clouds. This work has focused on the uptake kinetics for ammonia (NH3) and dinitrogen pentoxide (N2O5). The results of these investigations will be used to directly improve the representation of heterogeneous and multi-phase processes in global climate models, by identifying the key mechanistic drivers that control the variability in the observed kinetics.

  16. Angular Distributions of η Meson Production in pp Reactions

    NASA Astrophysics Data System (ADS)

    Fröhlich, I.; Balestra, F.; Bedfer, Y.; Bertini, R.; Bland, L. C.; Brenschede, A.; Brochard, F.; Bussa, M. P.; Choi, Seonho; Colantoni, M. L.; Dressler, R.; Dzemidzic, M.; Faivre, J.-Cl.; Ferrero, A.; Ferrero, L.; Foryciarz, J.; Frolov, V.; Garfagnini, R.; Grasso, A.; Heinz, S.; Jacobs, W. W.; Kühn, W.; Maggiora, A.; Maggiora, M.; Manara, A.; Panzieri, D.; Pfaff, H.-W.; Piragino, G.; Popov, A.; Ritman, J.; Salabura, P.; Tchalyshev, V.; Tosello, F.; Vigdor, S. E.; Zosi, G.

    With the DISTO spectrometer, exclusive η production in pp collisions have been measured at kinetic energies of Tbeam=2.15, 2.50 and 2.85 GeV, respectively, via the π+π-π0 decay channel. The resulting angular distributions of the η are important for the interpretation of dilepton spectra obtained in elementary as well as heavy ion reactions.

  17. ρ0 Meson Production in the pp Reactions with Disto

    NASA Astrophysics Data System (ADS)

    Salabura, P.; Balestra, F.; Bedfer, Y.; Bertini, R.; Bland, L. C.; Brenschede, A.; Brochard, F.; Bussa, M. P.; Choi, Seonho; Colantoni, M. L.; Dressler, R.; Dzemidzic, M.; Faivre, J.-Cl.; Ferrero, A.; Ferrero, L.; Foryciarz, J.; Fröhlich, I.; Frolov, V.; Garfagnini, R.; Grasso, A.; Heinz, S.; Jacobs, W. W.; Kühn, W.; Maggiora, A.; Maggiora, M.; Manara, A.; Panzieri, D.; Pfaff, H.-W.; Piragino, G.; Popov, A.; Ritman, J.; Tchalyshev, V.; Tosello, F.; Vigdor, S. E.; Zosi, G.

    2003-01-01

    Total and differential cross sections for the exclusive reaction pp → ppρ0 observed via the π+π- decay channel have been measured at pbeam= 3.67 GeV/c. The observed total meson production cross section is determined to be (23.4 ± 0.8 ± 8)μb and is significantly lower than typical cross sections used in model calculations for heavy ion collisions. The differential cross sections measured indicate a strong anisotropy ( ˜ \\cos2 θ ρ0^ CM) in the ρ0 meson production.

  18. Multi-strangeness production in hadron induced reactions

    NASA Astrophysics Data System (ADS)

    Gaitanos, T.; Moustakidis, Ch.; Lalazissis, G. A.; Lenske, H.

    2016-10-01

    We discuss in detail the formation and propagation of multi-strangeness particles in reactions induced by hadron beams relevant for the forthcoming experiments at FAIR. We focus the discussion on the production of the decuplet-particle Ω and study for the first time the production and propagation mechanism of this heavy hyperon inside hadronic environments. The transport calculations show the possibility of Ω-production in the forthcoming P ‾ANDA-experiment, which can be achieved with measurable probabilities using high-energy secondary Ξ-beams. We predict cross sections for Ω-production. The theoretical results are important in understanding the hyperon-nucleon and, in particular, the hyperon-hyperon interactions also in the high-strangeness sector. We emphasize the importance of our studies for the research plans at FAIR.

  19. [Preservation of bread and pastry products in a controlled atmosphere].

    PubMed

    Manchon, P

    1978-01-01

    Industrial soft pastries and the various breads are cereals products containing a humidity which is favorable to the development of mouldiness. Different or various methods of conservation has been attempted. One interesting approach to the problem is packaging in controlled atmosphere. It requires adequate machinery and suitable conditioning materials. Jardry-Buquet and Hayssen's machines are rapidly described as well as some of the packing film used for making air-tight bags. Bad results were observed with nitrogen, argon and a mixture of nitrogen-carbon dioxide. The satisfactory results obtained with the nitrous oxide for cakes (especially fruit-cakes) and for the bread with a mixture of ethylene oxide-carbon dioxide are: a good conservation for a period of 4 to 6 months in both cases. Organoleptic qualities of the products are not significantly diminished after eight weeks of preservation. The gases contained on the bags are analysed at different periods and the progressive disappearance of the nitrous oxide as well as the athylene dioxide was measured. The compounds derivated from these gases were researched on different extracts. No derivatives of the nitrous oxide were observed. From the ethylene oxide, the derivatives found in the bread are diethylene glycol and 2-chloroethanol; their concentrations are respectively 100 and 300 ppm in the case of 85 : 15 mixture, but decrease to a mere trace and 45 ppm in the case of 98 : 2 mixture. The measure of humidity, of peroxides and of the staleness of crumb are favourable for a good conservation.

  20. Attached Eddies and Production Spectra in the Atmospheric Logarithmic Layer

    NASA Astrophysics Data System (ADS)

    McNaughton, K. G.

    We investigate the production components of turbulent spectra within logarithmic layers over flat ground. This assumes that the turbulence giving rise to these spectra consists of active coherent structures (eddies) that are attached to the ground, and whose properties display perfect statistical self-similarity under inner scaling. That is, we take the extreme view that active coherent structures not only contribute to turbulence production spectra but explain the whole of them, so that neither detached eddies nor unstructured motions make any significant contribution. Perfect self-similarityis held to apply only to eddies that are themselves formed totally within the log layer, so the theory applies in the limit of spectra obtained at the hearts of very deep log layers. The model predicts that spectral variance and covariance should become independent of wavenumber at small wavenumbers. This asymptotic behaviour is observed in all neutral spectra from the Kansas experiment. The model also interprets the various positions of the spectral peaks observed at Kansas and in aircraft flights over the sea as consequences of the eddies being aggregated into files aligned with the wind. The observed spectra are therefore consistent with large-scale wedge-like structures being the principal component of active turbulence in the neutral atmospheric surface layer.

  1. Temperature- and pH-dependent aqueous-phase kinetics of the reactions of glyoxal and methylglyoxal with atmospheric amines and ammonium sulfate

    NASA Astrophysics Data System (ADS)

    Sedehi, Nahzaneen; Takano, Hiromi; Blasic, Vanessa A.; Sullivan, Kristin A.; De Haan, David O.

    2013-10-01

    Reactions of glyoxal (Glx) and methylglyoxal (MG) with primary amines and ammonium salts may produce brown carbon and N-containing oligomers in aqueous aerosol. 1H NMR monitoring of reactant losses and product appearance in bulk aqueous reactions were used to derive rate constants and quantify competing reaction pathways as a function of pH and temperature. Glx + ammonium sulfate (AS) and amine reactions generate products containing C-N bonds, with rates depending directly on pH: rate = (70 ± 60) M-1 s-1fAld [Glx]totfAm [Am]tot, where fAld is the fraction of aldehyde with a dehydrated aldehyde functional group, and fAm is the fraction of amine or ammonia that is deprotonated at a given pH. MG + amine reactions generate mostly aldol condensation products and exhibit less pH dependence: rate = 10[(0.36 ± 0.06) × pH - (3.6 ± 0.3)] M-1 s-1fAld [MG]tot [Am]tot. Aldehyde + AS reactions are less temperature-dependent (Ea = 18 ± 8 kJ mol-1) than corresponding amine reactions (Ea = 50 ± 11 kJ mol-1). Using aerosol concentrations of [OH] = 10-12 M, [amine]tot = [AS] = 0.1 M, fGlx = 0.046 and fMG = 0.09, we estimate that OH radical reactions are normally the major aerosol-phase sink for both dicarbonyl compounds. However, reactions with AS and amines together can account for up to 12 and 45% of daytime aerosol-phase glyoxal and methylglyoxal reactivity, respectively, in marine aerosol at pH 5.5. Reactions with AS and amines become less important in acidic or non-marine aerosol, but may still be significant atmospheric sources of brown carbon, imidazoles, and nitrogen-containing oligomers.

  2. Carbonyl products of the gas phase reaction of ozone with symmetrical alkenes

    SciTech Connect

    Grosjean, E.; Grosjean, D.

    1996-06-01

    In this study, carbonyl products have been identified and their yields measured in experiments involving the gas phase reaction of ozone with the eight symmetrical alkenes ethylene, cis-3-hexene, cis-4-octene, trans-4-octene, cis-5-decene, trans-5-decene, trans-2, 5-dimethyl-3-hexene, and (cis+trans)-3,4-dimethyl-3-hexene in purified air. Sufficient cyclohexane was added to scavenge the hydroxyl radical (OH) in order to minimize the reaction of OH with the alkenes and with their carbonyl products. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with simple reaction mechanism. Carbonyls other than the primary carbonyls R{sub 1}COR{sub 2} were identified as products. Their formation is discussed in terms of subsequent reactions of the R{sub 1}R{sub 2}COO biradicals CH{sub 3}CH{sub 2}CHOO, CH{sub 3}(CH{sub 2}){sub 2}CHOO, CH{sub 3}(CH{sub 2}){sub 3}CHOO, (CH{sub 3}){sub 2}CHCHOO, and C{sub 2}H{sub 5}C(CH{sub 3})OO. Similarities and differences are discussed for cis and trans isomers and for biradical reactions as a function of the nature and number of the substituents. The results are compared to those for the biradicals H{sub 2}COO, CH{sub 3}CHOO, and (CH{sub 3}){sub 2}COO from simpler symmetrical alkenes and contribute to a better understanding of the ozone-alkene reaction under atmospheric conditions. 51 refs., 1 fig., 3 tabs.

  3. Atmospheric chemical reactions of alternatives of polybrominated diphenyl ethers initiated by OH: A case study on triphenyl phosphate.

    PubMed

    Yu, Qi; Xie, Hong-Bin; Chen, Jingwen

    2016-11-15

    Many studies have been performed to evaluate the environmental risk caused by alternative flame retardants (AFRs) of polybrominated diphenyl ethers due to their ubiquitous occurrence in the environment. However, as an indispensable component of the environmental risk assessment, the information on atmospheric fate of AFRs is limited although some AFRs have been frequently and highly detected in the atmosphere. Here, a combined quantum chemical method and kinetics modeling were used to investigate atmospheric transformation mechanism and kinetics of AFRs initiated by OH in the presence of O2, taking triphenyl phosphate (TPhP) as a case. Results show that the pathway involving initial OH addition to phenyl of TPhP to form TPhP-OH adduct, and subsequent reaction of the TPhP-OH adduct with O2 to finally form phenol phosphate, is the most favorable for the titled reaction. The calculated overall reaction rate constant is 1.6×10(-12)cm(3) molecule(-1)s(-1), translating 7.6days atmospheric lifetime of TPhP. This clarifies that gaseous TPhP has atmospheric persistence. In addition, it was found that ice surface, as a case of ubiquitous water in the atmosphere, has little effect on the kinetics of the rate-determining step in the OH-initiated TPhP reaction. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. The Influence of Atmospheric Conditions on the Production of Ozone during VOC Oxidation

    NASA Astrophysics Data System (ADS)

    Coates, J.; Butler, T. M.

    2015-12-01

    Tropospheric ozone is a short-lived climate forcing pollutant that is detrimental to human health and crop growth. Reactions involving volatile organic compounds (VOC) and nitrogen oxides (NOx) in the presence of sunlight produce ozone. Ozone production is a non-linear function of the concentrations of both NOx and VOC, with VOC acting as the "fuel" for ozone production and NOx as the "catalyst". Different VOC, due to their differing structure and carbon content, have different maximum potential to produce ozone. Due to different degrees of reactivity, VOC also differ in the time taken to reach this maximum ozone production potential under ideal conditions. Ozone production is also influenced by meteorological factors such as radiation, temperature, advection and mixing, which may alter the rate of ozone production, and the degree to which VOC are able to reach their maximum ozone production potential. Identifying the chemical and meteorological processes responsible for controlling the degree to which VOC are able to reach their maximum ozone production potential could inform decisions on emission control to efficiently tackle high levels of tropospheric ozone. In this study we use a boxmodel to determine the chemical processes affecting ozone production under different meteorological and chemical conditions. The chemistry scheme used by the boxmodel is "tagged" for each initial VOC enabling attribution of ozone production to its VOC source. We systematically vary a number of meteorological parameters along with the source of NOx within the box model to simulate a range of atmospheric conditions. These simulations are compared with a control simulation done under conditions of maximum ozone formation to determine which parameters affect the rate at which VOC produce ozone and the extent to which they reach their maximum potential to produce ozone. We perform multi-day simulations in order to examine whether these processes can influence ozone production over

  5. Wind turbine power production and annual energy production depend on atmospheric stability and turbulence

    DOE PAGES

    St. Martin, Clara M.; Lundquist, Julie K.; Clifton, Andrew; ...

    2016-11-01

    Using detailed upwind and nacelle-based measurements from a General Electric (GE) 1.5sle model with a 77 m rotor diameter, we calculate power curves and annual energy production (AEP) and explore their sensitivity to different atmospheric parameters to provide guidelines for the use of stability and turbulence filters in segregating power curves. The wind measurements upwind of the turbine include anemometers mounted on a 135 m meteorological tower as well as profiles from a lidar. We calculate power curves for different regimes based on turbulence parameters such as turbulence intensity (TI) as well as atmospheric stability parameters such as the bulk Richardson number (RB). Wemore » also calculate AEP with and without these atmospheric filters and highlight differences between the results of these calculations. The power curves for different TI regimes reveal that increased TI undermines power production at wind speeds near rated, but TI increases power production at lower wind speeds at this site, the US Department of Energy (DOE) National Wind Technology Center (NWTC). Similarly, power curves for different RB regimes reveal that periods of stable conditions produce more power at wind speeds near rated and periods of unstable conditions produce more power at lower wind speeds. AEP results suggest that calculations without filtering for these atmospheric regimes may overestimate the AEP. Because of statistically significant differences between power curves and AEP calculated with these turbulence and stability filters for this turbine at this site, we suggest implementing an additional step in analyzing power performance data to incorporate effects of atmospheric stability and turbulence across the rotor disk.« less

  6. Wind turbine power production and annual energy production depend on atmospheric stability and turbulence

    SciTech Connect

    St. Martin, Clara M.; Lundquist, Julie K.; Clifton, Andrew; Poulos, Gregory S.; Schreck, Scott J.

    2016-11-01

    Using detailed upwind and nacelle-based measurements from a General Electric (GE) 1.5sle model with a 77 m rotor diameter, we calculate power curves and annual energy production (AEP) and explore their sensitivity to different atmospheric parameters to provide guidelines for the use of stability and turbulence filters in segregating power curves. The wind measurements upwind of the turbine include anemometers mounted on a 135 m meteorological tower as well as profiles from a lidar. We calculate power curves for different regimes based on turbulence parameters such as turbulence intensity (TI) as well as atmospheric stability parameters such as the bulk Richardson number (RB). We also calculate AEP with and without these atmospheric filters and highlight differences between the results of these calculations. The power curves for different TI regimes reveal that increased TI undermines power production at wind speeds near rated, but TI increases power production at lower wind speeds at this site, the US Department of Energy (DOE) National Wind Technology Center (NWTC). Similarly, power curves for different RB regimes reveal that periods of stable conditions produce more power at wind speeds near rated and periods of unstable conditions produce more power at lower wind speeds. AEP results suggest that calculations without filtering for these atmospheric regimes may overestimate the AEP. Because of statistically significant differences between power curves and AEP calculated with these turbulence and stability filters for this turbine at this site, we suggest implementing an additional step in analyzing power performance data to incorporate effects of atmospheric stability and turbulence across the rotor disk.

  7. Acid–base chemical reaction model for nucleation rates in the polluted atmospheric boundary layer

    PubMed Central

    Chen, Modi; Titcombe, Mari; Jiang, Jingkun; Jen, Coty; Kuang, Chongai; Fischer, Marc L.; Eisele, Fred L.; Siepmann, J. Ilja; Hanson, David R.; Zhao, Jun; McMurry, Peter H.

    2012-01-01

    Climate models show that particles formed by nucleation can affect cloud cover and, therefore, the earth's radiation budget. Measurements worldwide show that nucleation rates in the atmospheric boundary layer are positively correlated with concentrations of sulfuric acid vapor. However, current nucleation theories do not correctly predict either the observed nucleation rates or their functional dependence on sulfuric acid concentrations. This paper develops an alternative approach for modeling nucleation rates, based on a sequence of acid–base reactions. The model uses empirical estimates of sulfuric acid evaporation rates obtained from new measurements of neutral molecular clusters. The model predicts that nucleation rates equal the sulfuric acid vapor collision rate times a prefactor that is less than unity and that depends on the concentrations of basic gaseous compounds and preexisting particles. Predicted nucleation rates and their dependence on sulfuric acid vapor concentrations are in reasonable agreement with measurements from Mexico City and Atlanta. PMID:23091030

  8. Acid-base chemical reaction model for nucleation rates in the polluted atmospheric boundary layer.

    PubMed

    Chen, Modi; Titcombe, Mari; Jiang, Jingkun; Jen, Coty; Kuang, Chongai; Fischer, Marc L; Eisele, Fred L; Siepmann, J Ilja; Hanson, David R; Zhao, Jun; McMurry, Peter H

    2012-11-13

    Climate models show that particles formed by nucleation can affect cloud cover and, therefore, the earth's radiation budget. Measurements worldwide show that nucleation rates in the atmospheric boundary layer are positively correlated with concentrations of sulfuric acid vapor. However, current nucleation theories do not correctly predict either the observed nucleation rates or their functional dependence on sulfuric acid concentrations. This paper develops an alternative approach for modeling nucleation rates, based on a sequence of acid-base reactions. The model uses empirical estimates of sulfuric acid evaporation rates obtained from new measurements of neutral molecular clusters. The model predicts that nucleation rates equal the sulfuric acid vapor collision rate times a prefactor that is less than unity and that depends on the concentrations of basic gaseous compounds and preexisting particles. Predicted nucleation rates and their dependence on sulfuric acid vapor concentrations are in reasonable agreement with measurements from Mexico City and Atlanta.

  9. Reaction pathways for bio-active species in a He/H2O atmospheric pressure capacitive discharge

    NASA Astrophysics Data System (ADS)

    Ding, Ke; Lieberman, M. A.

    2015-01-01

    Helium/trace gas atmospheric pressure radio-frequency (rf) capacitive discharges have increasing biomedical applications. We have performed a principal pathway analysis for a chemically complex, bounded He/H2O atmospheric pressure, planar capacitive discharge, with a discharge gap of 0.5 mm and a power of 0.85 W cm-2 at 13.56 MHz (ne ≈ 1.6 × 1017 m-3). The discharge is embedded in a larger volume in which the H2O fraction is controlled to be 0.001. The generation and loss pathways for eleven species of interest for discharge maintenance and biomedical applications have been determined. The production and consumption pathways of He*, H2O, {{\\text{H}}11}\\text{O}5+ and electrons are found to be tightly coupled. The metastable He* generated by electron impact excitation of He is mostly consumed by Penning reactions with H2O, followed by subsequent three-body association reactions with H2O, to form the dominant positive ion, {{\\text{H}}11}\\text{O}5+ . The main loss pathways for {{\\text{H}}11}\\text{O}5+ are ion cluster fragmentations at the wall, which are important generation pathways for H2O. The generation and loss pathways for electrons are almost the same as for {{\\text{H}}11}\\text{O}5+ . OH and H2O2 generation and loss are strongly coupled, and they are important intermediate species in the generation pathways for the purely O-containing bio-active species: O2(a), O, O3 and O*. The generation and loss pathways for the latter four species were found to be strongly coupled by volume and surface processes, with O2 as an important precursor. The generation of O2 from H2O involves H2O2 as a key long-lived intermediate.

  10. Elementary reactions of N atoms with hydrocarbons: first steps towards the formation of prebiotic N-containing molecules in planetary atmospheres.

    PubMed

    Balucani, Nadia

    2012-08-21

    Gas-phase reactions involving atomic nitrogen in the ground (4)S and first excited (2)D electronic states with simple hydrocarbons or hydrocarbon radicals lead to the formation of prebiotic N-containing organic molecules. These reactions are now active in the upper atmosphere of Titan (a massive moon of Saturn) and might have played an important role in nitrogen fixation in the primitive upper terrestrial atmosphere, assuming that it is similar to the present atmosphere of Titan. The products of these reactions (nitriles, imines and radicals) are the precursors of larger N-containing molecules, which form the dense haze aerosols that completely cover the moon of Saturn. If anything similar to Titan's haze has ever existed on our planet, it is reasonable to imagine that, once deposited on the surface of the oceans, further chemical evolution might have transformed these molecules into aminoacids and nucleobases, the molecular building blocks of living entities. The experimental techniques necessary to investigate these reactions in detail are presented and the main results reviewed.

  11. Reaction products and mass balances from irradiated TCE vapor

    SciTech Connect

    Matthews, S.M.; Wang, F.T.; Mill, T.

    1995-12-31

    Trichloroethylene (TCE) vapor, at a concentration of 3000 ppmv in synthetic air, was sealed in Tedlar bags and irradiated with a 3.7 MeV electron beam. Bags of dry vapor and vapor at 90% relative humidity were irradiated. Doses up to 11 megarads (11 MR) were applied. Each bag was chemically analyzed for reaction products and a mass balance of the chlorine and carbon was obtained within the 11 MR dose range. The results of these radiolysis experiments and chemical analysis show that, given the proper treatment, the TCE concentration is reduced to below detection limit and the reaction products of the organic carbon and chlorine are carbon monoxide (CO), carbon dioxide (CO{sub 2}), chlorine gas (Cl{sub 2}) and hydrochloric acid (140). No detectable amounts of dichloroacetyl chloride (DCAC) or phosgene (PG) remained in the sample after proper treatment. DCAC and PG were found only as intermediary oxidation products of the TCE. High energy ionizing radiation, as electron beams and bremsstrahlung, is a new treatment technology for destroying toxic compounds and hazardous Wastes. A demonstration of complete destruction of organic products, using this treatment at standard temperature and pressure, is expected to help implement the use of this technology.

  12. An experimental kinetic study and products research of the reactions of O3 with a series of unsaturated alcohols

    NASA Astrophysics Data System (ADS)

    Chen, Yi; Wang, Jing; Zhao, Sanping; Tong, Shengrui; Ge, Maofa

    2016-11-01

    The gas-phase reactions of unsaturated alcohols with O3 were investigated in FEP Teflon film chamber at 298 K and 760 torr of atmosphere pressure. The rate constants of the reactions of C6-C8 alkenols with O3 were determined using both the absolute and the relative rate method, and the measured values were (5.96 ± 0.35) × 10-17 cm3 molecule-1 s-1 for (Z)-3-hexen-1-ol, (5.12 ± 0.30) × 10-17 cm3 molecule-1 s-1 for (Z)-3-hepten-1-ol, and (5.66 ± 0.52) × 10-17 cm3 molecule-1 s-1 for (Z)-3-octen-1-ol, respectively. The gas-phase products of these reactions mentioned above were detected using proton-transfer-reaction mass spectrum (PTR-MS). HOCH2CH2CHO, CH2CH2CHO, HCHO and CH3CHO were identified as the main gas products for (Z)-3-hexen-1-ol. HOCH2CH2CHO and CH3(CH2)2CHO dominated the gaseous products for (Z)-3-hepten-1-ol. And for (Z)-3-octen-1-ol, CH3(CH2)3CHO, CH3(CH2)2CHO and HOCH2CH2CHO were the main gaseous products. The SOA yields were monitored at the same time, which were 0.184 ± 0.013, 0.213 ± 0.017, 0.232 ± 0.021 for (Z)-3-hexen-1-ol, (Z)-3-hepten-1-ol and (Z)-3-octen-1-ol, respectively. The possible reaction mechanisms were proposed and discussed. The kinetic data presented here has been used to estimate their atmosphere lifetimes and the reaction reactivity. The atmosphere implication of these reactions has also been discussed.

  13. Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Worsnop, Douglas R.; Nelson, David D.; Zahniser, Mark S.

    1993-01-01

    IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

  14. Heterogeneous reaction of particulate chlorpyrifos with NO3 radicals: Products, pathways, and kinetics

    NASA Astrophysics Data System (ADS)

    Li, Nana; Zhang, Peng; Yang, Bo; Shu, Jinian; Wang, Youfeng; Sun, Wanqi

    2014-08-01

    Chlorpyrifos is a typical chlorinated organophosphorus pesticide. The heterogeneous reaction of chlorpyrifos particles with NO3 radicals was investigated using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and a real-time atmospheric gas analysis mass spectrometer. Chlorpyrifos oxon, 3,5,6-trichloro-2-pyridinol, O,O-diethyl O-hydrogen phosphorothioate, O,O-diethyl ester thiophosphoric acid, diethyl hydrogen phosphate and a phosphinyl disulfide compound were identified as the main degradation products. The heterogeneous reaction pathways were proposed and their kinetic processes were investigated via a mixed-phase relative rate method. The observed effective rate constant is 3.4 ± 0.2 × 10-12 cm3 molecule-1 s-1.

  15. Production and decay of baryonic resonances in pion induced reactions

    NASA Astrophysics Data System (ADS)

    Przygoda, Witold

    2016-11-01

    Pion induced reactions give unique opportunities for an unambiguous description of baryonic resonances and their coupling channels. A systematic energy scan and high precision data, in conjunction with a partial wave analysis, allow for the study of the excitation function of the various contributions. A review of available world data unravels strong need for modern facilities delivering measurements with a pion beam. Recently, HADES collaboration collected data in pion-induced reactions on light (12C) and heavy (74W) nuclei at a beam momentum of 1.7 GeV/c dedicated to strangeness production. It was followed by a systematic scan at four different pion beam momenta (0.656, 0.69, 0.748 and 0.8 GeV/c) in π- - p reaction in order to tackle the role of N(1520) resonance in conjunction with the intermediate ρ production. First results on exclusive channels with one pion (π- p) and two pions (nπ+π-, pπ-π0) in the final state are discussed.

  16. A study of switchgrass pyrolysis: Product variability and reaction kinetics

    NASA Astrophysics Data System (ADS)

    Bovee, Jonathan Matthew

    Samples of the same cultivar of cave-in-rock switchgrass were harvested from plots in Frankenmuth, Roger City, Cass County, and Grand Valley, Michigan. It was determined that variation exists, between locations, among the pyrolytic compounds which can lead to variability in bio-oil and increased processing costs at bio-refineries to make hydrocarbon fuels. Washed and extractives-free switchgrass samples, which contain a lower alkali and alkaline earth metals content than untreated samples, were shown to produce lower amounts of acids, esters, furans, ketones, phenolics, and saccharides and also larger amounts of aldehydes upon pyrolysis. Although the minerals catalyzed pyrolytic reactions, there was no evidence indicating their effect on reducing the production of anhydrosugars, specifically levoglucosan. To further link minerals present in the biomass to a catalytic pathway, mathematic models were employed to determine the kinetic parameters of the switchgrass. While the calculated activation energies of switchgrass, using the FWO and KAS methods, were 227.7 and 217.8 kJ/mol, correspondingly, it was concluded that the activation energies for the switchgrass hemicellulose and cellulose peaks were 115.5 and 158.2 kJ/mol, respectively, using a modified model-fitting method. The minerals that effect the production of small molecules and levoglucosan also have an observable catalytic effect on switchgrass reaction rate, which may be quantifiable through the use of reaction kinetics so as to determine activation energy.

  17. Flow reactor and triple quadrupole mass spectrometer investigations of negative ion reactions involving nitric acid - Implications for atmospheric HNO3 detection by chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Moehler, O.; Arnold, F.

    1991-07-01

    The ion-molecule reactions on which Active Chemical Ionization Mass Spectrometry (ACIMS) measurements of atmospheric nitric acid are based are presently subjected to product-ion distribution and rate coefficient measurements. The results obtained indicate that while previous stratospheric nitric acid measurements were not impared by collisional dissociation processes, these processes may have played a major role during previous tropospheric measurements: leading to an undereestimation of nitric acid concentrations. A novel ACIMS ion source has been developed in order to avoid these problems.

  18. Production of medical 99 m Tc isotope via photonuclear reaction

    NASA Astrophysics Data System (ADS)

    Fujiwara, M.; Nakai, K.; Takahashi, N.; Hayakawa, T.; Shizuma, T.; Miyamoto, S.; Fan, G. T.; Takemoto, A.; Yamaguchi, M.; Nishimura, M.

    2017-01-01

    99 m Tc with a 6 hour half-life is one of the most important medical isotopes used for the Single-Photon Emission Computed Tomography (SPECT) inspection in hospitals of US, Canada, Europe and Japan. 99 m Tc isotopes are extracted by the milking method from parent 99Mo isotopes with a 66 hour half-life. The supply of 99Mo isotopes now encounters a serious crisis. Hospitals may not suitably receive 99Mo medical isotopes in near future, due to difficulties in production by research nuclear reactors. Many countries are now looking for alternative ways to generate 99Mo isotopes other than those with research reactors. We discuss a sustained availability of 99 m Tc isotopes via the nat Mo(γ, n) photonuclear reaction, and discuss to solve technical problems for extracting pure 99 m Tc isotopes from other output materials of photonuclear reactions.

  19. Water Catalysis of the Reaction between Methanol and OH at 294 K and the Atmospheric Implications.

    PubMed

    Jara-Toro, Rafael A; Hernández, Federico J; Taccone, Raúl A; Lane, Silvia I; Pino, Gustavo A

    2017-02-13

    The rate coefficient for the reaction CH3 OH+OH was determined by means of a relative method in a simulation chamber under quasi-real atmospheric conditions (294 K, 1 atm of air) and variable humidity or water concentration. Under these conditions, a quadratic dependence of the rate coefficient for the reaction CH3 OH+OH on the water concentration was found. Thus the catalytic effect of water is not only important at low temperatures, but also at room temperature. The detailed mechanism responsible of the reaction acceleration is still unknown. However, this dependence should be included in the atmospheric global models since it is expected to be important in humid regions as in the tropics. Additionally, it could explain several differences regarding the global and local atmospheric concentration of methanol in tropical areas, for which many speculations about the sinks and sources of methanol have been reported.

  20. Agroecosystem productivity in a warmer and CO2 enriched atmosphere

    NASA Astrophysics Data System (ADS)

    Bernacchi, Carl; Köhler, Iris; Ort, Donald; Long, Steven; Clemente, Thomas

    2017-04-01

    A number of in-field manipulative experiments have been conducted that address the response of key ecosystem services of major agronomic species to rising CO2. Global warming, however, is inextricably linked to rising greenhouse gases in general, of which CO2 is the most dominant. Therefore, agroecosystem functioning in future conditions requires an understanding of plant responses to both rising CO2 and increased temperatures. Few in-field manipulative experiments have been conducted that supplement both heating and CO2 above background concentrations. Here, the results of six years of experimentation using a coupled Free Air CO2 Enrichment (FACE) technology with variable output infrared heating arrays are reported. The manipulative experiment increased temperatures (+ 3.5˚ C) and CO2 (+ 200 μmol mol-1) above background levels for on two major agronomic crop species grown throughout the world, Zea mays (maize) and Glycine max (soybean). The first phase of this research addresses the response of plant physiological parameters to growth in elevated CO2 and warmer temperatures for maize and soybean grown in an open-air manipulative experiment. The results show that any increase in ecosystem productivity associated with rising CO2 is either similar or is offset by growth at higher temperatures, inconsistent with the perceived benefits of higher CO2 plus warmer temperatures on agroecosystem productivity. The second phase of this research addresses the opportunity to genetically modify soybean to allow for improved productivity under high CO2 and warmer temperatures by increasing a key photosynthetic carbon reduction cycle enzyme, SPBase. The results from this research demonstrates that manipulation of the photosynthetic pathway can lead to higher productivity in high CO2 and temperature relative to the wild-type control soybean. Overall, this research advances the understanding of the physiological responses of two major crops, and the impact on ecosystem services

  1. Atmospheric emission of reactive nitrogen during biofuel ethanol production.

    PubMed

    Machado, Cristine M D; Cardoso, Arnaldo A; Allen, Andrew G

    2008-01-15

    This paper evaluates emissions to the atmosphere of biologically available nitrogen compounds in a region characterized by intensive sugar cane biofuel ethanol production. Large emissions of NH3 and NOx, as well as particulate nitrate and ammonium, occur at the harvest when the crop is burned, with the amount of nitrogen released equivalent to approximately 35% of annual fertilizer-N application. Nitrogen oxides concentrations show a positive association with fire frequency, indicating that biomass burning is a major emission source, with mean concentrations of NOx doubling in the dry season relative to the wetseason. During the dry season biomass burning is a source of NH3, with other sources (wastes, soil, biogenic) predominant during the wet season. Estimated NO2-N, NH3-N, NO3- -N and NH4+ -N emission fluxes from sugar cane burning in a planted area of ca. 2.2 x 10(6) ha are 11.0, 1.1, 0.2, and 1.2 Gg N yr(-1), respectively.

  2. Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

    NASA Technical Reports Server (NTRS)

    Payne, W. A.; Nava, D. F.; Brunning, J.; Stief, L. J.

    1986-01-01

    The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

  3. Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

    NASA Technical Reports Server (NTRS)

    Payne, W. A.; Nava, D. F.; Brunning, J.; Stief, L. J.

    1986-01-01

    The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

  4. Theoretical aspects of product formation from the NCO + NO reaction

    SciTech Connect

    Lin, M.C.; He, Y. ); Melius, C.F. )

    1993-09-09

    The reaction of NCO with NO, an important elementary process involved in the reduction of NO[sub x] by HNCO, has been studied theoretically using the BAC-MP4 technique in conjunction with RRKM calculations. The computed molecular structures and thermochemical data for various intermediates and transition states suggest that the reaction takes place primarily via the singlet, ground electronic state OCNNO molecule according to the following mechanism; (step a) NCO + NO [leftrightarrow] [sup 1]OCNNO [yields] N[sub 2]O + CO; (step b) NCO + NO [leftrightarrow] [sup 1]OCNNO [yields] c-OCNNO[minus] N[sub 2] + CO[sub 2]. The formation of N[sub 2]O + CO occurs by the fragmentation of the singlet OCNNO intermediate step (a), whereas the production of N[sub 2] + CO[sub 2] by cyclization-fragmentation occurs via step b. The tight transition states leading to the formation of these products, coupled with the loose entrance channel, give rise to the experimentally observed strong negative temperature dependence which can be quantitatively accounted for by the results of RRKM calculations based on the BAC-MP4 data. The experimentally measured product branching ratio for channels a and b could be accounted for theoretically by lowering the calculated energy barrier for step a by 3.6 kcal/mol, corresponding to about 15% of the barrier height. 22 refs., 3 figs., 5 tabs.

  5. Infrared absorption strengths of potential gaseous diffusion plant coolants and related reaction products

    SciTech Connect

    Trowbridge, L.D.; Angel, E.C.

    1993-05-01

    The DOE gaseous diffusion plant complex makes extensive use of CFC-114 as a primary coolant. As this material is scheduled for production curtailment within the next few years, a search for substitutes is underway, and apparently workable alternatives have been found and are under testing. The presently favored substitutes, FC-c3l8 and FC-3110, satisfy ozone depletion and operational chemical compatibility concerns, but will be long-lived greenhouse gases, and thus may be regulated on that basis in the future. A further search is therefore underway for compounds with shorter atmospheric lifetimes which could otherwise satisfy operational physical and chemical requirements. A number of such candidates are in the process of being screened for chemical compatibility in a fluorinating environment. This document presents infrared spectral data developed and used in that study for candidates recently examined, and also for many of their fluorination reaction products. The data include gas-phase infrared spectra, quantitative peak intensities as a function of partial pressure, and integrated absorbance strength in the IR-transparent atmospheric window of interest to global warming modeling. Combining this last property with literature or estimated atmospheric lifetimes, rough estimates of global warming potential for these compounds are also presented.

  6. Manifestation of macroscopic correlations in elementary reaction kinetics. I. Irreversible reaction A +A→product

    NASA Astrophysics Data System (ADS)

    Doktorov, Alexander B.; Kipriyanov, Alexander A.; Kipriyanov, Alexey A.

    2010-05-01

    Using an modern many-particle method for the derivation of non-Markovian binary kinetic equations, we have treated theoretically the applicability of the encounter theory (ET) (the prototype of the collision theory) concepts to the widely known diffusion assisted irreversible bulk reaction A +A→product (for example, radical reaction) in dilute solutions. The method shows that the agreement with the ET is observed when the familiar integral ET is employed which in this method is just a step in the derivation of kinetic equations. It allows for two-particle correlations only, but fails to take account of correlation of reactant simultaneously with the partner of the encounter and the reactant in the bulk. However, the next step leading to the modified ET under transformation of equations to the regular form both extends the time range of the applicability of ET rate equation (as it was for reactions proceeding with one of the reactants in excess), and gives the equation of the generalized ET. In full agreement with physical considerations, this theory reveals macroscopic correlations induced by the encounters in the reservoir of free walks. This means that the encounters of reactants in solution are correlated on a rather large time interval of the reaction. Though any nonstationary (non-Markovian) effects manifest themselves rather weakly in the kinetics of the bimolecular reaction in question, just the existence of the revealed macroscopic correlations in the binary theory is of primary importance. In particular, it means that the well-known phenomena which are generally considered to be associated solely with correlation of particles on the encounter (for example, chemically induced dynamic nuclear polarization) may be induced by correlation in the reservoir of free random walks of radicals in solution.

  7. Manifestation of macroscopic correlations in elementary reaction kinetics. I. Irreversible reaction A+A-->product.

    PubMed

    Doktorov, Alexander B; Kipriyanov, Alexander A; Kipriyanov, Alexey A

    2010-05-28

    Using an modern many-particle method for the derivation of non-Markovian binary kinetic equations, we have treated theoretically the applicability of the encounter theory (ET) (the prototype of the collision theory) concepts to the widely known diffusion assisted irreversible bulk reaction A+A-->product (for example, radical reaction) in dilute solutions. The method shows that the agreement with the ET is observed when the familiar integral ET is employed which in this method is just a step in the derivation of kinetic equations. It allows for two-particle correlations only, but fails to take account of correlation of reactant simultaneously with the partner of the encounter and the reactant in the bulk. However, the next step leading to the modified ET under transformation of equations to the regular form both extends the time range of the applicability of ET rate equation (as it was for reactions proceeding with one of the reactants in excess), and gives the equation of the generalized ET. In full agreement with physical considerations, this theory reveals macroscopic correlations induced by the encounters in the reservoir of free walks. This means that the encounters of reactants in solution are correlated on a rather large time interval of the reaction. Though any nonstationary (non-Markovian) effects manifest themselves rather weakly in the kinetics of the bimolecular reaction in question, just the existence of the revealed macroscopic correlations in the binary theory is of primary importance. In particular, it means that the well-known phenomena which are generally considered to be associated solely with correlation of particles on the encounter (for example, chemically induced dynamic nuclear polarization) may be induced by correlation in the reservoir of free random walks of radicals in solution.

  8. Atmospheric Oxidation of Two Isoprene By-Products, Hydroxyacetone and Glycolaldehyde

    NASA Astrophysics Data System (ADS)

    Orlando, J. J.; Tyndall, G. S.; Taraborrelli, D.

    2012-12-01

    Hydroxyacetone [CH3C(=O)CH2OH, HYAC] and glycolaldehyde [GLYALD, HOCH2CH=O] are common multi-functional oxygenated VOC compounds, formed as first- and second-generation products of isoprene oxidation. Reaction with OH is expected to be the major gas-phase loss for both species, leading to a lifetime of about one day for GLYALD and 3 days for HYAC. Recent studies by Butkovskaya et al. (1,2) indicate that oxidation of these species by OH might lead to significant yields of formic and acetic acids, particularly at reduced temperature. To confirm these data, we have conducted a study of HYAC and GLYALD oxidation, using environmental chamber / FTIR techniques. Experiments show that direct organic acid production from HYAC is minimal over a range of temperatures (248-298 K) under NOx-free chamber conditions. Formic acid production in the presence of NOx does occur, but at higher NOx levels than normally encountered in the atmosphere. In addition, preliminary results for GLYALD indicate limited formic acid production in the absence of NOx (270-298 K). Product yield data for both species over a range of temperatures and conditions, and mechanistic interpretation of the data will be presented with focus on newer data on GLYALD.

  9. The effects of heterogeneous reactions on atmospheric chemistry and aerosol properties

    NASA Astrophysics Data System (ADS)

    Wei, Chao; Carmichael, Gregory; Su, Hang; Cheng, Yafang

    2017-04-01

    A new aerosol module is developed for the STEM model (the Sulfur Transport and dEposition Model) to better understand the chemical aging of dust during long range transport and assess the impact of heterogeneous reactions on tropospheric chemistry. The new aerosol module is verified and first applied in a box model, and then coupled into the 3-Dimentional STEM model. In the new aerosol model, a nonequilibrium (dynamic or kinetic) approach to treat gas-to-particle conversion is employed to replace the equilibrium method in STEM model. Meanwhile, a new numerical method solving the aerosol dynamics equation is introduced into the dynamic aerosol model for its improved computational efficiency and high accuracy. Compared with the equilibrium method, the new dynamic approach is found to provide better results on predicating the different hygroscopicity and chemical aging patterns as a function of size. The current modeling study also takes advantage of new findings from laboratory experiments about heterogeneous reactions on mineral oxides and dust particles, in order to consider the complexity of surface chemistry (such as surface saturation, coating and relative humidity). Modeling results show that the impacts of mineralogy and relative humidity on heterogeneous reactions are significant and should be considered in atmospheric chemistry modeling with first priority. The new dynamic approach for gas-to-particle conversion and RH-dependent heterogeneous uptake of HNO3 improve the model performance in term of aerosol predictions under different conditions. It is shown that these improvements change the modeled nitrate and sulfate concentrations, but also modify their size distributions significantly.

  10. Isotope modeling of nitric acid formation in the atmosphere: Testing the importance of NO oxidation, heterogeneous reactions, and nighttime chemistry

    NASA Astrophysics Data System (ADS)

    Michalski, G.; Xu, F.

    2009-12-01

    Atmospheric nitrate (NO3-atm = HNO3 and particulate nitrate) is the primary sink of NOx and its isotopic composition can yield important information about oxidation pathways. In particular oxygen isotope anomalies, the 17O excess (Δ17O values), have potential to determine the relative importance of NOx oxidation pathways (OH, NO3 or N2O5). We have developed a new isotope tracer model to test whether Δ17O is a viable tracer for heterogeneous N2O5 hydrolysis and or NO3 radical reactions. The model uses the Regional Atmospheric Chemical Mechanism (RACM) and the isotope mass balance transfer mechanism we previously suggested. RACM was modified to account for heterogeneous uptake using three different parameterization schemes. We then conducted a sensitivity analysis that varied trace gas concentrations (NOx, VOC’s, biogenic organics), aerosol properties (mass, composition), and meteorology (RH, temperature, solar flux) and monitored the Δ17O values in NO3-atm product. The model predicts that under most conditions, NO3-atm Δ17O values are between 19 and 34‰ in agreement with observations. The model predicts that the D17O value in NO3-atm should have temperature dependence, as well as a seasonal effect. There was a small, but significant difference in predicted Δ17O values based on which N2O5 hydrolysis scheme was used suggesting that Δ17O analysis of NO3-atm may be a way of validating which scheme is most accurately reflecting the actual chemistry of the atmosphere. The model output results suggest that the oxidation pathway of NO3 to NO2, either by ozone or by peroxy radicals, has a pronounced impact on the resulting Δ17O values and can lead to Δ17O values lower than those observed in the existing data sets (8-18‰). There is a strong correlation between NO oxidation pathway and Δ17O value in NO3-atm. The accuracy of the predictions of Δ17O values made by the model can be tested by selecting unique environments and collecting NO3-atm then analyzing it

  11. Prompt HO2 formation following the reaction of OH with aromatic compounds under atmospheric conditions.

    PubMed

    Nehr, Sascha; Bohn, Birger; Wahner, Andreas

    2012-06-21

    The secondary formation of HO(2) radicals following OH + aromatic hydrocarbon reactions in synthetic air under normal pressure and temperature was investigated in the absence of NO after pulsed production of OH radicals. OH and HO(x) (=OH + HO(2)) decay curves were recorded using laser-induced fluorescence after gas-expansion. The prompt HO(2) yields (HO(2) formed without preceding NO reactions) were determined by comparison to results obtained with CO as a reference compound. This approach was recently introduced and applied to the OH + benzene reaction and was extended here for a number of monocyclic aromatic hydrocarbons. The measured HO(2) formation yields are as follows: toluene, 0.42 ± 0.11; ethylbenzene, 0.53 ± 0.10; o-xylene, 0.41 ± 0.08; m-xylene, 0.27 ± 0.06; p-xylene, 0.40 ± 0.09; 1,2,3-trimethylbenzene, 0.31 ± 0.06; 1,2,4-trimethylbenzene, 0.37 ± 0.09; 1,3,5-trimethylbenzene, 0.29 ± 0.08; hexamethylbenzene, 0.32 ± 0.08; phenol, 0.89 ± 0.29; o-cresol, 0.87 ± 0.29; 2,5-dimethylphenol, 0.72 ± 0.12; 2,4,6-trimethylphenol, 0.45 ± 0.13. For the alkylbenzenes HO(2) is the proposed coproduct of phenols, epoxides, and possibly oxepins formed in secondary reactions with O(2). In most product studies the only quantified coproducts were phenols whereas only a few studies reported yields of epoxides. Oxepins have not been observed so far. Together with the yields of phenols from other studies, the HO(2) yields determined in this work set an upper limit to the combined yields of epoxides and oxepins that was found to be significant (≤0.3) for all investigated alkylbenzenes except m-xylene. For the hydroxybenzenes the currently proposed HO(2) coproducts are dihydroxybenzenes. For phenol and o-cresol the determined HO(2) yields are matching the previously reported dihydroxybenzene yields, indicating that these are the only HO(2) forming reaction channels. For 2,5-dimethylphenol and 2,4,6-trimethylphenol no complementary product studies are available.

  12. Electrochemical product detection of an asymmetric convective polymerase chain reaction.

    PubMed

    Duwensee, Heiko; Mix, Maren; Stubbe, Marco; Gimsa, Jan; Adler, Marcel; Flechsig, Gerd-Uwe

    2009-10-15

    For the first time, we describe the application of heated microwires for an asymmetric convective polymerase chain reaction (PCR) in a modified PCR tube in a small volume. The partly single-stranded product was labeled with the electrochemically active compound osmium tetroxide bipyridine using a partially complementary protective strand with five mismatches compared to the single-stranded product. The labeled product could be successfully detected at a gold electrode modified with a complementary single-stranded capture probe immobilized via a thiol-linker. Our simple thermo-convective PCR yielded electrochemically detectable products after only 5-10 min. A significant discrimination between complementary and non-complementary target was possible using different immobilized capture probes. The total product yield was approx. half the amount of the classical thermocycler PCR. Numerical simulations describing the thermally driven convective PCR explain the received data. Discrimination between complementary capture probes and non-complementary capture probes was performed using square-wave voltammetry. The coupling of asymmetric thermo-convective PCR with electrochemical detection is very promising for future compact DNA sensor devices.

  13. State-to-state quantum dynamics of O + O2 isotope exchange reactions reveals nonstatistical behavior at atmospheric conditions.

    PubMed

    Sun, Zhigang; Liu, Lan; Lin, Shi Ying; Schinke, Reinhard; Guo, Hua; Zhang, Dong H

    2010-01-12

    The O + O(2) exchange reaction is a prerequisite for the formation of ozone in Earth's atmosphere. We report here state-to-state differential and integral cross sections for several O + O(2) isotope-exchange reactions obtained by dynamically exact quantum scattering calculations at collision energies relevant to atmospheric conditions. These reactions are shown to be highly nonstatistical, evidenced by dominant forward scattering and deviation of the integral cross section from the statistical limit. Mechanistic analyses revealed that the nonstatistical channel is facilitated by short-lived osculating resonances. The theoretical results provided an in-depth interpretation of a recent molecular beam experiment of the exchange reaction and shed light on the initial step of ozone recombination.

  14. Isomer ratios for products of photonuclear reactions on 121Sb

    NASA Astrophysics Data System (ADS)

    Bezshyyko, Oleg; Dovbnya, Anatoliy; Golinka-Bezshyyko, Larisa; Kadenko, Igor; Vodin, Oleksandr; Olejnik, Stanislav; Tuller, Gleb; Kushnir, Volodymyr; Mitrochenko, Viktor

    2017-09-01

    Over the past several years various preequilibrium model approaches for nuclear reactions were developed. Diversified detailed experimental data in the medium excitation energy region for nucleus are needed for reasonable selection among these theoretical models. Lack of experimental data in this energy region does essentially limit the possibilities for analysis and comparison of different preequilibrium theoretical models. For photonuclear reactions this energy region extends between bremsstrahlung energies nearly 30-100 MeV. Experimental measurements and estimations of isomer ratios for products of photonuclear reactions with multiple particle escape on antimony have been performed using bremsstrahlung with end-point energies 38, 43 and 53 MeV. Method of induced activity measurement was applied. For acquisition of gamma spectra we used HPGe spectrometer with 20% efficiency and energy resolution 1.9 keV for 1332 keV gamma line of 60Co. Linear accelerator of electrons LU-40 was a source of bremsstrahlung. Energy resolution of electron beam was about 1% and mean current was within (3.8-5.3) μA.

  15. Experimental measurements of low temperature rate coefficients for neutral-neutral reactions of interest for atmospheric chemistry of Titan, Pluto and Triton: reactions of the CN radical.

    PubMed

    Morales, Sébastien B; Le Picard, Sébastien D; Canosa, André; Sims, Ian R

    2010-01-01

    The kinetics of the reactions of cyano radical, CN (X2sigma+) with three hydrocarbons, propane (CH3CH2CH3), propene (CH3CH=CH2) and 1-butyne (CH[triple band]CCH2CH3) have been studied over the temperature range of 23-298 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. These reactions are of interest for the cold atmospheres of Titan, Pluto and Triton, as they might participate in the formation of nitrogen and carbon bearing molecules, including nitriles, that are thought to play an important role in the formation of hazes and biological molecules. All three reactions are rapid with rate coefficients in excess of 10(-10) cm3 molecule(-1) s(-1) at the lowest temperatures of this study and show behaviour characteristic of barrierless reactions. Temperature dependences, different for each reaction, are compared to those used in the most recent photochemical models of Titan's atmosphere.

  16. Hydrogen shift reactions in four methyl-buten-ol (MBO) peroxy radicals and their impact on the atmosphere

    NASA Astrophysics Data System (ADS)

    Knap, Hasse C.; Schmidt, Johan A.; Jørgensen, Solvejg

    2016-12-01

    We investigate the hydrogen shift (H-shift) reactions in the peroxy radicals derived from four different methyl-buten-ol (MBO) molecules; 2-methyl-3-buten-2-ol (MBO232), 2-methyl-3-buten-1-ol (MBO231), 3-Methyl-3-buten-2-ol (MBO332) and 3-methyl-3-buten-1-ol (MBO331), with quantum mechanical calculations. The rate constants of the 1,5 H-shift reactions in all four MBO peroxy radicals are greater than the rate constants of the 1,4 or 1,6 H-shift reactions. The rate constants for the 1,5 H-shift reaction from either a CH group or an OH group are approximately 1 s-1 and 10-3 s-1, respectively. The atmospheric impact of the MBO232 oxidation is investigated with the global chemical transport model (GEOS-Chem). The 1,4-CH and 1,5-OH H-shift reactions in the MBO232 peroxy radical play a minor role with a total yield of about 2%. The major atmospheric reactions of the MBO232 peroxy radical are the reactions with NO and HO2, with reaction yield of 85% and 13%, respectively.

  17. Studies of Elementary Reactions of Chemical Importance in the Atmospheres of Planets

    NASA Technical Reports Server (NTRS)

    Nesbitt, Fred L.

    2003-01-01

    The paper discusses the following: 1. F + Cl2 Kinetics. Absolute rate constant for the reaction F(P-2) with Cl2 has been measured using the discharge flow kinetics technique coupled to mass spectrometric detection at T = 180 - 360 K and 1 Torr He nominal pressure. 2. Vapor pressure system. The main effort on the vapor pressure system involved the design and construction of an insulated enclosure ("Bakeout Box") to improve the uniformity of heating during the bakeout process. 3. Sunphotometer System. This period saw the completion of the two-channel sunphotometer, its calibration, and two field deployments. 4. Vibrational-to-translation (V-T) transfer rates for light hydrocarbons at low temperatures are important parameters in thermal-structure models of the upper atmospheres of the outer planets and their satellites. However, the required data are either simply not available or do not extend to the low temperatures found in those systems. Because methane is such an important constituent in outer planet atmospheres, we have initiated a program to measure the temperature dependence of (V-T) rates for its relaxation by appropriate collision partners. 5. The central focus of this research has been the vapor phase nucleation and growth of metals/refractory species into small particles and the aggregation of these primary particles into larger structures. These topics are part of the broader goal of understanding the conditions under which interstellar dust grains condense from stellar outflows and how these small dust grains coagulate into larger bodies such as planetesimals or planets.

  18. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification.

    PubMed

    Li, Jianhua; Peng, Jianbiao; Zhang, Ya; Ji, Yuefei; Shi, Huanhuan; Mao, Liang; Gao, Shixiang

    2016-06-05

    This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H2O2 concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H2O2 concentration, while the optimal pH and H2O2 concentration were 7.0 and 8μM, respectively. 98% TCS was removed with only 0.1UmL(-1) SBP in 30min reaction time, while an HRP dose of 0.3UmL(-1) was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (KCAT) and catalytic efficiency (KCAT/KM) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via CC and CO coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water/wastewater treatment.

  19. Kinetics and products study of the reaction of BrO radicals with gaseous mercury

    NASA Astrophysics Data System (ADS)

    Raofie, F.; Ariya, P. A.

    2003-05-01

    Bro reactions of elemental mercury was as a major candidate for near complete depletion of elemental mercury in polar region. The kinetics of the reaction between BrO radicals with gaseous mercury was identified using relative rate method by Gas Chromatography with Mass spectroscopic Detection (GC-MS) at room temperature (298±1 K) and at atmospheric pressure 760 ± 1 Torr in the N_2 diluent. Propane, DMS and butane were used as reference molecules. The upper and lower limits rate constant for reaction of Hg^0 with BrO was estimated to be 1.0 × 10^{-13} and 1.0 × 10^{15} cm^3 molecules^{-1} s^{-1}, respectively. BrO radicals were produced from the photolysis of bromine and dibromomethane in presence of ozone and detected by MS at m/e = 95 or 97. Ozone was produced in a Silent discharged generator. Reaction products were identified using direct mass spectrometer with chemical ionization ion source.

  20. Comprehensive atmospheric modeling of reactive cyclic siloxanes and their oxidation products

    NASA Astrophysics Data System (ADS)

    Janechek, Nathan J.; Hansen, Kaj M.; Stanier, Charles O.

    2017-07-01

    Cyclic volatile methyl siloxanes (cVMSs) are important components in personal care products that transport and react in the atmosphere. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and their gas-phase oxidation products have been incorporated into the Community Multiscale Air Quality (CMAQ) model. Gas-phase oxidation products, as the precursor to secondary organic aerosol from this compound class, were included to quantify the maximum potential for aerosol formation from gas-phase reactions with OH. Four 1-month periods were modeled to quantify typical concentrations, seasonal variability, spatial patterns, and vertical profiles. Typical model concentrations showed parent compounds were highly dependent on population density as cities had monthly averaged peak D5 concentrations up to 432 ng m-3. Peak oxidized D5 concentrations were significantly less, up to 9 ng m-3, and were located downwind of major urban areas. Model results were compared to available measurements and previous simulation results. Seasonal variation was analyzed and differences in seasonal influences were observed between urban and rural locations. Parent compound concentrations in urban and peri-urban locations were sensitive to transport factors, while parent compounds in rural areas and oxidized product concentrations were influenced by large-scale seasonal variability in OH.

  1. Atmospheric CO2 uptake throughout bio-enhanced brucite-water reaction at Montecastelli serpentinites (Italy)

    NASA Astrophysics Data System (ADS)

    Bedini, Federica; Boschi, Chiara; Ménez, Benedicte; Perchiazzi, Natale; Zanchetta, Giovanni

    2014-05-01

    In the last several years, interactions between microorganisms and minerals have intrigued and catched the interest of the scientific community. Montecastelli serpentinites (Tuscany, Italy) are characterized by CO2-mineral carbonation, an important process which leads to spontaneous formation of carbonate phases uptaking atmospheric CO2. In the studied areas carbonate precipitates, mainly hydrated Mg-carbonates, are present in form of crusts, coating and spherules on exposed rock surfaces, and filling rock fractures. Petrographic and mineralogical observations revealed that Tuscan brucite-rich serpentinites hosts preserve their original chemical compositions with typical mesh-textured serpentine (± brucite) after olivine, magnetite-rich mesh rims and relicts of primary spinel. Representative hydrated carbonate samples have been collected in three different areas and analyzed to investigate the role of biological activity and its influence in the serpentine-hydrated Mg-carbonates reaction. The different types of whitish precipitates have been selected under binocular microscope for XRD analyses performed at the Dipartimento di Scienze della Terra (University of Pisa, Italy): their mineralogical composition consists of mainly hydromagnesite and variable amount of other metastable carbonate phases (i.e. nesquehonite, manasseite, pyroaurite, brugnatellite and aragonite). Moreover, the crystallinity analysis of whitish crust and spherules have been carried out by detailed and quantitative XRD analyses to testify a possible biologically controlled growth, inasmuch as the crystal structure of biominerals could be affected by many lattice defects (i.e. dislocations, twinning, etc.) and this observation cause low crystallinity of the mineral. The presence of microbial cells and relicts of organic matter has already been detected by confocal laser scanning microscopy (CLSM) combined with Raman spectromicroscopy in a previous study (Bedini et al., 2013). The presence of

  2. Water-soluble reaction products from ozonolysis of grasses

    SciTech Connect

    Morrison, W.H. III; Akin, D.E. )

    1990-03-01

    Ozone has been used to pretreat agricultural byproducts with the aim of increasing nutritive value for ruminants. However, not all treatments with ozone result in enhanced digestibility, suggesting reaction products from ozone treatment of plants might inhibit rumen microbial activity. Coastal Bermuda grass (Cynodon dactylon L. Pers.) (CBG) and Kentucky-31 tall fescue (Festuca arundinacea Schreb.) (K-31) were treated with ozone and the water-soluble products determined. The following acids were identified: caproic, levulinic, p-hydroxybenzoic, vinillic, azelaic, and malonic. In addition, vanillin and p-hydroxybenzaldehyde were also identified. Ozone treatment of the cell walls of CBG produced mainly p-hydroxybenzoic acid, vanillic acid, azelaic acid, p-hydroxybenzaldehyde, and vanillin. Ozone treatment of K-31 cell walls produced levulinic acid in addition to those products found from CBG cell walls. The production of vanillin and p-hydroxybenzaldehyde, which have been shown to be especially toxic to rumen microorganisms, offers an explanation for the negative affects of ozone treatment on forage.

  3. Effect of reaction atmosphere on particle morphology of TiO2 produced by thermal decomposition of titanium tetraisopropoxide

    NASA Astrophysics Data System (ADS)

    Choi, Jae Gil; Park, Kyun Young

    2006-04-01

    Thermal decomposition of titanium tetraisopropoxide (TTIP) was carried out in varying reaction atmospheres: nitrogen, oxygen, and nitrogen plus water vapor. The effect of reaction atmosphere on the morphology, size, and crystalline structure of produced TiO2 particles was studied. The reactor used was similar to the microreactor proposed earlier by Park et al. (2001, J. Nanopart. Res., 3, 309-319), but for a modification in the precursor evaporator. The reactor temperature was varied from 300 to 700°C and the TTIP concentration in the evaporator from 1.0 to 7.0 mol%, holding the reactor residence time at 0.7 s. The primary-particle size was in the range 25-250 nm, varying with operating condition. The crystalline structure was amorphous in nitrogen, a mixture of rutile and anatase in nitrogen plus water vapor, and anatase in oxygen atmospheres. In nitrogen, agglomerates composed of very small particles whose individual boundaries are not clearly distinguished were produced. In oxygen, the particles composing an agglomerate became larger and were clearly spherical. As the atmosphere was varied to the nitrogen plus water vapor, the particle size increased further. The variation of primary particle size with reaction atmosphere was discussed in comparison with previous experimental data.

  4. H + CD4 abstraction reaction dynamics: product energy partitioning.

    PubMed

    Hu, Wenfang; Lendvay, György; Troya, Diego; Schatz, George C; Camden, Jon P; Bechtel, Hans A; Brown, Davida J A; Martin, Marion R; Zare, Richard N

    2006-03-09

    This paper presents experimental and theoretical studies of the product energy partitioning associated with the H + CD4 (nu = 0) --> HD + CD3 reaction for the collision energy range 0.5-3.0 eV. The theoretical results are based on quasiclassical trajectories from (1) first principles direct dynamics calculations (B3LYP/6-31G), (2) an empirical surface developed by Espinosa-García [J. Chem. Phys. 2002, 116, 10664] (EG), and (3) two semiempirical surfaces (MSINDO and reparametrized MSINDO). We find that most of the energy appears in product translation at energies just above the reactive threshold; however, HD vibration and rotation become quite important at energies above 1 eV, each accounting for over 20% of the available energy above 1.5 eV, according to the B3LYP calculations. The barrier on the B3LYP surface, though being later than that on EG, predicts significantly higher HD vibrational excitation than EG. This deviation is contradictory to what would be expected on the basis of the Polanyi rules and derives from modest differences in the potential energy surfaces. The CD3 internal energy is generally quite low, and we present detailed rotational state distributions which show that the CD3 rotational distribution is largely independent of collision energy in the 0.75-1.95 eV range. The most populated rotational levels are N = 5 and 6 on B3LYP, with most of that excitation being associated with motion about the C2 axes, rather than C3 axis, of the CD3 product, in good agreement with the experimental results. Through our extensive studies in this and previous work concerning the scattering dynamics, we conclude that B3LYP/6-31G provides the best available description of the overall dynamics for the title reaction at relatively high collision energies.

  5. Computations and estimates of rate coefficients for hydrocarbon reactions of interest to the atmospheres of outer solar system

    NASA Technical Reports Server (NTRS)

    Laufer, A. H.; Gardner, E. P.; Kwok, T. L.; Yung, Y. L.

    1983-01-01

    The rate coefficients, including Arrhenius parameters, have been computed for a number of chemical reactions involving hydrocarbon species for which experimental data are not available and which are important in planetary atmospheric models. The techniques used to calculate the kinetic parameters include the Troe and semiempirical bond energy-bond order (BEBO) or bond strength-bond length (BSBL) methods.

  6. POLYCHLORINATED DIBENZO-P-DIOXINS AND DIBENZOFURANS: GAS-PHASE HYDROXYL RADICAL REACTIONS AND RELATED ATMOSPHERIC REMOVAL. (R825377)

    EPA Science Inventory

    Gas-phase reactions with the hydroxyl radical (OH) are
    expected to be an important removal pathway of polychlorinated dibenzo-p-dioxins and dibenzofurans
    (PCDD/F)
    in the atmosphere. Our laboratory recently developed
    a system to measure the rate constants of ...

  7. POLYCHLORINATED DIBENZO-P-DIOXINS AND DIBENZOFURANS: GAS-PHASE HYDROXYL RADICAL REACTIONS AND RELATED ATMOSPHERIC REMOVAL. (R825377)

    EPA Science Inventory

    Gas-phase reactions with the hydroxyl radical (OH) are
    expected to be an important removal pathway of polychlorinated dibenzo-p-dioxins and dibenzofurans
    (PCDD/F)
    in the atmosphere. Our laboratory recently developed
    a system to measure the rate constants of ...

  8. Computations and estimates of rate coefficients for hydrocarbon reactions of interest to the atmospheres of outer solar system

    NASA Technical Reports Server (NTRS)

    Laufer, A. H.; Gardner, E. P.; Kwok, T. L.; Yung, Y. L.

    1983-01-01

    The rate coefficients, including Arrhenius parameters, have been computed for a number of chemical reactions involving hydrocarbon species for which experimental data are not available and which are important in planetary atmospheric models. The techniques used to calculate the kinetic parameters include the Troe and semiempirical bond energy-bond order (BEBO) or bond strength-bond length (BSBL) methods.

  9. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed.

    PubMed

    Gaikwad, Vaibhav; Kennedy, Eric; Mackie, John; Holdsworth, Clovia; Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael; Dlugogorski, Bogdan

    2014-09-15

    In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  10. A Kinetic Study of the Gas Phase Neutral-Neutral Reactions Between Sulfur- and Chlorine-Containing Molecules Present in the Atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Maffucci, D. M.; Woon, D. E.; Herbst, E.

    2017-05-01

    Using updated electronic structures, we employ a variety of kinetic theories to calculate the reaction rate constants for neutral-neutral chemical reactions between sulfur- and chlorine-containing molecules observed in the atmosphere of Venus.

  11. Paramagnetic products of the reaction of hydrogen atoms with sodium azide

    SciTech Connect

    Vasil'ev, A.A.; Lisetskii, V.N.; Kulikov, N.F.; Savel'ev, G.G.

    1987-09-01

    The reaction of hydrogen atoms with sodium azide in high-frequency discharges has been postulated to lead to NaNH and molecular nitrogen as reaction products. This article investigates these products via electron spin resonance spectroscopy. Data are given on reaction and ionization kinetics as well as on the electronic structure and hyperfine interaction of the products.

  12. 40 CFR 721.4461 - Hydrofluoric acid, reaction products with octane (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrofluoric acid, reaction products... New Uses for Specific Chemical Substances § 721.4461 Hydrofluoric acid, reaction products with octane... identified generically as a hydrofluoric acid, reaction products with octane (PMN P-99-0052) is subject to...

  13. 40 CFR 721.4461 - Hydrofluoric acid, reaction products with octane (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrofluoric acid, reaction products... New Uses for Specific Chemical Substances § 721.4461 Hydrofluoric acid, reaction products with octane... identified generically as a hydrofluoric acid, reaction products with octane (PMN P-99-0052) is subject to...

  14. 40 CFR 721.4461 - Hydrofluoric acid, reaction products with octane (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrofluoric acid, reaction products... New Uses for Specific Chemical Substances § 721.4461 Hydrofluoric acid, reaction products with octane... identified generically as a hydrofluoric acid, reaction products with octane (PMN P-99-0052) is subject to...

  15. 40 CFR 721.10428 - Fatty acids, C18-unsatd., dimers, reaction products with 1-piperazineethanamine.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., reaction products with 1-piperazineethanamine. 721.10428 Section 721.10428 Protection of Environment..., reaction products with 1-piperazineethanamine. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as fatty acids, C18-unsatd., dimers, reaction products...

  16. 40 CFR 721.9514 - Ethyl silicate, reaction products with modified alkoxysilane salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ethyl silicate, reaction products with... Significant New Uses for Specific Chemical Substances § 721.9514 Ethyl silicate, reaction products with.... (1) The chemical substance identified generically as Ethyl silicate, reaction products with...

  17. 40 CFR 721.4461 - Hydrofluoric acid, reaction products with octane (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrofluoric acid, reaction products... New Uses for Specific Chemical Substances § 721.4461 Hydrofluoric acid, reaction products with octane... identified generically as a hydrofluoric acid, reaction products with octane (PMN P-99-0052) is subject...

  18. 40 CFR 721.9265 - Reaction product of dichlorobenzidine and substituted alkylamide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of dichlorobenzidine... Significant New Uses for Specific Chemical Substances § 721.9265 Reaction product of dichlorobenzidine and... substance identified generically as a reaction product of dichlorobenzidine and substituted alkylamide...

  19. 40 CFR 721.10445 - 2-Propen-1-ol, reaction products with hydrogen sulfide, distn. residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 2-Propen-1-ol, reaction products with... Significant New Uses for Specific Chemical Substances § 721.10445 2-Propen-1-ol, reaction products with...) The chemical substance identified as 2-propen-1-ol, reaction products with hydrogen sulfide,...

  20. 40 CFR 721.4461 - Hydrofluoric acid, reaction products with octane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrofluoric acid, reaction products... New Uses for Specific Chemical Substances § 721.4461 Hydrofluoric acid, reaction products with octane... identified generically as a hydrofluoric acid, reaction products with octane (PMN P-99-0052) is subject...

  1. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  2. 40 CFR 721.10154 - Quaternary ammonium compounds, dicoco alkyldimethyl, chlorides, reaction products with silica.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... alkyldimethyl, chlorides, reaction products with silica. 721.10154 Section 721.10154 Protection of Environment..., dicoco alkyldimethyl, chlorides, reaction products with silica. (a) Chemical substance and significant..., dicoco alkyldimethyl, chlorides, reaction products with silica (PMN P-08-157; CAS No. 956147-76-5)...

  3. 40 CFR 721.2582 - Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of alkylene diamine... Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine (generic). (a... generically as reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and...

  4. 40 CFR 721.4385 - Hydrofluoric acid, reaction products with heptane.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrofluoric acid, reaction products... Specific Chemical Substances § 721.4385 Hydrofluoric acid, reaction products with heptane. (a) Chemical... hydrofluoric acid, reaction products with heptane (PMN P-98-1036; CAS No. 207409-71-0) is subject to...

  5. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  6. 40 CFR 721.2582 - Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of alkylene diamine... Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine (generic). (a... generically as reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and...

  7. 40 CFR 721.10154 - Quaternary ammonium compounds, dicoco alkyldimethyl, chlorides, reaction products with silica.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... alkyldimethyl, chlorides, reaction products with silica. 721.10154 Section 721.10154 Protection of Environment..., dicoco alkyldimethyl, chlorides, reaction products with silica. (a) Chemical substance and significant..., dicoco alkyldimethyl, chlorides, reaction products with silica (PMN P-08-157; CAS No. 956147-76-5)...

  8. 40 CFR 721.9265 - Reaction product of dichlorobenzidine and substituted alkylamide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of dichlorobenzidine... Significant New Uses for Specific Chemical Substances § 721.9265 Reaction product of dichlorobenzidine and... substance identified generically as a reaction product of dichlorobenzidine and substituted alkylamide...

  9. 40 CFR 721.4385 - Hydrofluoric acid, reaction products with heptane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrofluoric acid, reaction products... Specific Chemical Substances § 721.4385 Hydrofluoric acid, reaction products with heptane. (a) Chemical... hydrofluoric acid, reaction products with heptane (PMN P-98-1036; CAS No. 207409-71-0) is subject to...

  10. 40 CFR 721.10358 - Formaldehyde reaction products with aryl amine (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Formaldehyde reaction products with... New Uses for Specific Chemical Substances § 721.10358 Formaldehyde reaction products with aryl amine... identified generically as formaldehyde reaction products with aryl amine (PMN P-09-546) is subject...

  11. 40 CFR 721.9285 - Reaction products of formalin (37%) with amine C12.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction products of formalin (37... Specific Chemical Substances § 721.9285 Reaction products of formalin (37%) with amine C12. (a) Chemical... as reaction products of formalin (37%) with amine C12 (PMN P-95-535) is subject to reporting...

  12. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  13. 40 CFR 721.10464 - Fatty acid, reaction products with alkanolamine (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Fatty acid, reaction products with... Specific Chemical Substances § 721.10464 Fatty acid, reaction products with alkanolamine (generic). (a... generically as fatty acid, reaction products with alkanolamine (PMN P-03-461) is subject to reporting...

  14. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  15. 40 CFR 721.10301 - Reaction products of fatty alcohols, (aminoethylaminopropyl) dialkoxymethylsilane, glycidol, and...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction products of fatty alcohols... Substances § 721.10301 Reaction products of fatty alcohols, (aminoethylaminopropyl) dialkoxymethylsilane... uses subject to reporting. (1) The chemical substance identified generically as reaction products...

  16. 40 CFR 721.10484 - Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., hydroxy-terminated, reaction products with -modified silica. 721.10484 Section 721.10484 Protection of... Silicones, Me vinyl, hydroxy-terminated, reaction products with -modified silica. (a) Chemical substance and..., Me vinyl, hydroxy-terminated, reaction products with -modified silica (PMN P-04-432; CAS No....

  17. 40 CFR 721.9485 - Dimer acid/polymerized rosin amidoamine reaction product (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... amidoamine reaction product (generic). 721.9485 Section 721.9485 Protection of Environment ENVIRONMENTAL... reaction product (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as Dimer acid/polymerized rosin amidoamine reaction product...

  18. 40 CFR 721.10212 - 1,2-Ethanediol, reaction products with epichlorohydrin.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false 1,2-Ethanediol, reaction products with... Specific Chemical Substances § 721.10212 1,2-Ethanediol, reaction products with epichlorohydrin. (a... 1,2-ethanediol, reaction products with epichlorohydrin (PMN P-09-241; CAS No. 705265-31-2)...

  19. 40 CFR 721.9265 - Reaction product of dichlorobenzidine and substituted alkylamide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of dichlorobenzidine... Significant New Uses for Specific Chemical Substances § 721.9265 Reaction product of dichlorobenzidine and... substance identified generically as a reaction product of dichlorobenzidine and substituted alkylamide...

  20. 40 CFR 721.9285 - Reaction products of formalin (37%) with amine C12.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction products of formalin (37... Specific Chemical Substances § 721.9285 Reaction products of formalin (37%) with amine C12. Link to an... to reporting. (1) The chemical substance identified generically as reaction products of formalin...

  1. 40 CFR 721.10154 - Quaternary ammonium compounds, dicoco alkyldimethyl, chlorides, reaction products with silica.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... alkyldimethyl, chlorides, reaction products with silica. 721.10154 Section 721.10154 Protection of Environment..., dicoco alkyldimethyl, chlorides, reaction products with silica. (a) Chemical substance and significant..., dicoco alkyldimethyl, chlorides, reaction products with silica (PMN P-08-157; CAS No. 956147-76-5)...

  2. 40 CFR 721.10154 - Quaternary ammonium compounds, dicoco alkyldimethyl, chlorides, reaction products with silica.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... alkyldimethyl, chlorides, reaction products with silica. 721.10154 Section 721.10154 Protection of Environment..., dicoco alkyldimethyl, chlorides, reaction products with silica. (a) Chemical substance and significant..., dicoco alkyldimethyl, chlorides, reaction products with silica (PMN P-08-157; CAS No. 956147-76-5)...

  3. 40 CFR 721.9485 - Dimer acid/polymerized rosin amidoamine reaction product (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... amidoamine reaction product (generic). 721.9485 Section 721.9485 Protection of Environment ENVIRONMENTAL... reaction product (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as Dimer acid/polymerized rosin amidoamine reaction product...

  4. 40 CFR 721.10358 - Formaldehyde reaction products with aryl amine (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Formaldehyde reaction products with... New Uses for Specific Chemical Substances § 721.10358 Formaldehyde reaction products with aryl amine... identified generically as formaldehyde reaction products with aryl amine (PMN P-09-546) is subject...

  5. 40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... reaction products with mixed metal oxides (generic). 721.10574 Section 721.10574 Protection of Environment... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (PMN P-09-48) is subject to reporting under this section for...

  6. 40 CFR 721.9285 - Reaction products of formalin (37%) with amine C12.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction products of formalin (37... Specific Chemical Substances § 721.9285 Reaction products of formalin (37%) with amine C12. (a) Chemical... as reaction products of formalin (37%) with amine C12 (PMN P-95-535) is subject to reporting...

  7. 40 CFR 721.10445 - 2-Propen-1-ol, reaction products with hydrogen sulfide, distn. residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 2-Propen-1-ol, reaction products with... Significant New Uses for Specific Chemical Substances § 721.10445 2-Propen-1-ol, reaction products with...) The chemical substance identified as 2-propen-1-ol, reaction products with hydrogen sulfide,...

  8. 40 CFR 721.10360 - 1-Substituted propane, 3-(triethoxysilyl)-, reaction products with polyethylene glycol mono...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-(triethoxysilyl)-, reaction products with polyethylene glycol mono-(branched tridecyl) ether (generic). 721.10360... Substances § 721.10360 1-Substituted propane, 3-(triethoxysilyl)-, reaction products with polyethylene glycol...)-, reaction products with polyethylene glycol mono-(branched tridecyl) ether (PMN P-09-628) is subject...

  9. 40 CFR 721.2582 - Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of alkylene diamine... Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine (generic). (a... generically as reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and...

  10. 40 CFR 721.9285 - Reaction products of formalin (37%) with amine C12.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction products of formalin (37... Specific Chemical Substances § 721.9285 Reaction products of formalin (37%) with amine C12. (a) Chemical... as reaction products of formalin (37%) with amine C12 (PMN P-95-535) is subject to reporting...

  11. 40 CFR 721.2582 - Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylene diamine... Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine (generic). (a... generically as reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and...

  12. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  13. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  14. 40 CFR 721.9285 - Reaction products of formalin (37%) with amine C12.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction products of formalin (37... Specific Chemical Substances § 721.9285 Reaction products of formalin (37%) with amine C12. (a) Chemical... as reaction products of formalin (37%) with amine C12 (PMN P-95-535) is subject to reporting...

  15. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  16. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  17. 40 CFR 721.4385 - Hydrofluoric acid, reaction products with heptane.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrofluoric acid, reaction products... Specific Chemical Substances § 721.4385 Hydrofluoric acid, reaction products with heptane. (a) Chemical... hydrofluoric acid, reaction products with heptane (PMN P-98-1036; CAS No. 207409-71-0) is subject to...

  18. 40 CFR 721.9514 - Ethyl silicate, reaction products with modified alkoxysilane salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ethyl silicate, reaction products with... Significant New Uses for Specific Chemical Substances § 721.9514 Ethyl silicate, reaction products with.... (1) The chemical substance identified generically as Ethyl silicate, reaction products with...

  19. 40 CFR 721.8085 - Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of substituted... Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated (generic). (a... generically as reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

  20. 40 CFR 721.10358 - Formaldehyde reaction products with aryl amine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Formaldehyde reaction products with... New Uses for Specific Chemical Substances § 721.10358 Formaldehyde reaction products with aryl amine... identified generically as formaldehyde reaction products with aryl amine (PMN P-09-546) is subject...

  1. 40 CFR 721.2582 - Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylene diamine... Reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and alkylamine (generic). (a... generically as reaction product of alkylene diamine, MDl, substituted carbomonocyclic amine and...

  2. 40 CFR 721.10240 - Olefinic carbocycle, reaction products with alkoxysilane (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Olefinic carbocycle, reaction products... Significant New Uses for Specific Chemical Substances § 721.10240 Olefinic carbocycle, reaction products with... substance identified generically as olefinic carbocycle, reaction products with alkoxysilane (PMN...

  3. 40 CFR 721.10428 - Fatty acids, C18-unsatd., dimers, reaction products with 1-piperazineethanamine.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., reaction products with 1-piperazineethanamine. 721.10428 Section 721.10428 Protection of Environment..., reaction products with 1-piperazineethanamine. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as fatty acids, C18-unsatd., dimers, reaction products...

  4. 40 CFR 721.10212 - 1,2-Ethanediol, reaction products with epichlorohydrin.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false 1,2-Ethanediol, reaction products with... Specific Chemical Substances § 721.10212 1,2-Ethanediol, reaction products with epichlorohydrin. (a... 1,2-ethanediol, reaction products with epichlorohydrin (PMN P-09-241; CAS No. 705265-31-2)...

  5. 40 CFR 721.8085 - Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of substituted... Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated (generic). (a... generically as reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

  6. 40 CFR 721.9485 - Dimer acid/polymerized rosin amidoamine reaction product (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... amidoamine reaction product (generic). 721.9485 Section 721.9485 Protection of Environment ENVIRONMENTAL... reaction product (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as Dimer acid/polymerized rosin amidoamine reaction product...

  7. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  8. 40 CFR 721.10251 - Fatty acids, reaction products with alkanolamine (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Fatty acids, reaction products with... Specific Chemical Substances § 721.10251 Fatty acids, reaction products with alkanolamine (generic). (a... generically as fatty acids, reaction products with alkanolamine (PMN P-09-366) is subject to reporting...

  9. 40 CFR 721.9514 - Ethyl silicate, reaction products with modified alkoxysilane salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethyl silicate, reaction products with... Significant New Uses for Specific Chemical Substances § 721.9514 Ethyl silicate, reaction products with.... (1) The chemical substance identified generically as Ethyl silicate, reaction products with...

  10. 40 CFR 721.9485 - Dimer acid/polymerized rosin amidoamine reaction product (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... amidoamine reaction product (generic). 721.9485 Section 721.9485 Protection of Environment ENVIRONMENTAL... reaction product (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as Dimer acid/polymerized rosin amidoamine reaction product...

  11. 40 CFR 721.10484 - Siloxanes and Silicones, Me vinyl, hydroxy-terminated, reaction products with...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., hydroxy-terminated, reaction products with -modified silica. 721.10484 Section 721.10484 Protection of... Silicones, Me vinyl, hydroxy-terminated, reaction products with -modified silica. (a) Chemical substance and..., Me vinyl, hydroxy-terminated, reaction products with -modified silica (PMN P-04-432; CAS No....

  12. 40 CFR 721.4385 - Hydrofluoric acid, reaction products with heptane.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrofluoric acid, reaction products... Specific Chemical Substances § 721.4385 Hydrofluoric acid, reaction products with heptane. (a) Chemical... hydrofluoric acid, reaction products with heptane (PMN P-98-1036; CAS No. 207409-71-0) is subject to...

  13. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  14. 40 CFR 721.4385 - Hydrofluoric acid, reaction products with heptane.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrofluoric acid, reaction products... Specific Chemical Substances § 721.4385 Hydrofluoric acid, reaction products with heptane. (a) Chemical... hydrofluoric acid, reaction products with heptane (PMN P-98-1036; CAS No. 207409-71-0) is subject to...

  15. 40 CFR 721.10251 - Fatty acids, reaction products with alkanolamine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Fatty acids, reaction products with... Specific Chemical Substances § 721.10251 Fatty acids, reaction products with alkanolamine (generic). (a... generically as fatty acids, reaction products with alkanolamine (PMN P-09-366) is subject to reporting...

  16. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  17. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  18. 40 CFR 721.10212 - 1,2-Ethanediol, reaction products with epichlorohydrin.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false 1,2-Ethanediol, reaction products with... Specific Chemical Substances § 721.10212 1,2-Ethanediol, reaction products with epichlorohydrin. (a... 1,2-ethanediol, reaction products with epichlorohydrin (PMN P-09-241; CAS No. 705265-31-2)...

  19. 40 CFR 721.10360 - 1-Substituted propane, 3-(triethoxysilyl)-, reaction products with polyethylene glycol mono...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-(triethoxysilyl)-, reaction products with polyethylene glycol mono-(branched tridecyl) ether (generic). 721.10360... Substances § 721.10360 1-Substituted propane, 3-(triethoxysilyl)-, reaction products with polyethylene glycol...)-, reaction products with polyethylene glycol mono-(branched tridecyl) ether (PMN P-09-628) is subject...

  20. 40 CFR 721.10301 - Reaction products of fatty alcohols, (aminoethylaminopropyl) dialkoxymethylsilane, glycidol, and...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction products of fatty alcohols... Substances § 721.10301 Reaction products of fatty alcohols, (aminoethylaminopropyl) dialkoxymethylsilane... uses subject to reporting. (1) The chemical substance identified generically as reaction products...

  1. 40 CFR 721.10240 - Olefinic carbocycle, reaction products with alkoxysilane (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Olefinic carbocycle, reaction products... Significant New Uses for Specific Chemical Substances § 721.10240 Olefinic carbocycle, reaction products with... substance identified generically as olefinic carbocycle, reaction products with alkoxysilane (PMN...

  2. 40 CFR 721.8085 - Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of substituted... Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated (generic). (a... generically as reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

  3. 40 CFR 721.10360 - 1-Substituted propane, 3-(triethoxysilyl)-, reaction products with polyethylene glycol mono...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-(triethoxysilyl)-, reaction products with polyethylene glycol mono-(branched tridecyl) ether (generic). 721.10360... Substances § 721.10360 1-Substituted propane, 3-(triethoxysilyl)-, reaction products with polyethylene glycol...)-, reaction products with polyethylene glycol mono-(branched tridecyl) ether (PMN P-09-628) is subject...

  4. 40 CFR 721.10251 - Fatty acids, reaction products with alkanolamine (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Fatty acids, reaction products with... Specific Chemical Substances § 721.10251 Fatty acids, reaction products with alkanolamine (generic). (a... generically as fatty acids, reaction products with alkanolamine (PMN P-09-366) is subject to reporting...

  5. 40 CFR 721.2625 - Reaction product of alkane-diol and epichlorohydrin.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of alkane-diol and... Specific Chemical Substances § 721.2625 Reaction product of alkane-diol and epichlorohydrin. (a) Chemical... as reaction product of alkanediol and epichlorohydrin (PMN P-89-760) is subject to reporting...

  6. 40 CFR 721.9265 - Reaction product of dichlorobenzidine and substituted alkylamide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of dichlorobenzidine... Significant New Uses for Specific Chemical Substances § 721.9265 Reaction product of dichlorobenzidine and... substance identified generically as a reaction product of dichlorobenzidine and substituted alkylamide...

  7. 40 CFR 721.10494 - Reaction product of trimethylolpropane triacrylate and alkylene imine (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of trimethylolpropane... Significant New Uses for Specific Chemical Substances § 721.10494 Reaction product of trimethylolpropane.... (1) The chemical substance identified generically as reaction product of...

  8. 40 CFR 721.3805 - Formaldehyde, reaction products with 1,3-benzenedimethanamine and bisphenol A.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Formaldehyde, reaction products with 1... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3805 Formaldehyde, reaction products... to reporting. (1) The chemical substance identified as formaldehyde, reaction products with...

  9. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  10. 40 CFR 721.10574 - Alkylcarboxy polyester acrylate reaction products with mixed metal oxides (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... reaction products with mixed metal oxides (generic). 721.10574 Section 721.10574 Protection of Environment... reaction products with mixed metal oxides (generic). (a) Chemical substance and significant new uses... reaction products with mixed metal oxides (PMN P-09-48) is subject to reporting under this section for...

  11. 40 CFR 721.9265 - Reaction product of dichlorobenzidine and substituted alkylamide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of dichlorobenzidine... Significant New Uses for Specific Chemical Substances § 721.9265 Reaction product of dichlorobenzidine and... substance identified generically as a reaction product of dichlorobenzidine and substituted alkylamide...

  12. 40 CFR 721.10212 - 1,2-Ethanediol, reaction products with epichlorohydrin.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false 1,2-Ethanediol, reaction products with... Specific Chemical Substances § 721.10212 1,2-Ethanediol, reaction products with epichlorohydrin. (a... 1,2-ethanediol, reaction products with epichlorohydrin (PMN P-09-241; CAS No. 705265-31-2)...

  13. 40 CFR 721.10494 - Reaction product of trimethylolpropane triacrylate and alkylene imine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of trimethylolpropane... Significant New Uses for Specific Chemical Substances § 721.10494 Reaction product of trimethylolpropane.... (1) The chemical substance identified generically as reaction product of...

  14. 40 CFR 721.9514 - Ethyl silicate, reaction products with modified alkoxysilane salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ethyl silicate, reaction products with... Significant New Uses for Specific Chemical Substances § 721.9514 Ethyl silicate, reaction products with.... (1) The chemical substance identified generically as Ethyl silicate, reaction products with...

  15. 40 CFR 721.10390 - Acetoacetanilide reaction product with multifunctional acrylate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Acetoacetanilide reaction product with... New Uses for Specific Chemical Substances § 721.10390 Acetoacetanilide reaction product with... chemical substance identified generically as acetoacetanilide reaction product with...

  16. 40 CFR 721.10390 - Acetoacetanilide reaction product with multifunctional acrylate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Acetoacetanilide reaction product with... New Uses for Specific Chemical Substances § 721.10390 Acetoacetanilide reaction product with... chemical substance identified generically as acetoacetanilide reaction product with...

  17. 40 CFR 721.10464 - Fatty acid, reaction products with alkanolamine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Fatty acid, reaction products with... Specific Chemical Substances § 721.10464 Fatty acid, reaction products with alkanolamine (generic). (a... generically as fatty acid, reaction products with alkanolamine (PMN P-03-461) is subject to reporting...

  18. 40 CFR 721.9514 - Ethyl silicate, reaction products with modified alkoxysilane salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ethyl silicate, reaction products with... Significant New Uses for Specific Chemical Substances § 721.9514 Ethyl silicate, reaction products with.... (1) The chemical substance identified generically as Ethyl silicate, reaction products with...

  19. 40 CFR 721.10240 - Olefinic carbocycle, reaction products with alkoxysilane (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Olefinic carbocycle, reaction products... Significant New Uses for Specific Chemical Substances § 721.10240 Olefinic carbocycle, reaction products with... substance identified generically as olefinic carbocycle, reaction products with alkoxysilane (PMN...

  20. 40 CFR 721.8085 - Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of substituted... Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated (generic). (a... generically as reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

  1. 40 CFR 721.10301 - Reaction products of fatty alcohols, (aminoethylaminopropyl) dialkoxymethylsilane, glycidol, and...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction products of fatty alcohols... Substances § 721.10301 Reaction products of fatty alcohols, (aminoethylaminopropyl) dialkoxymethylsilane... uses subject to reporting. (1) The chemical substance identified generically as reaction products...

  2. 40 CFR 721.10390 - Acetoacetanilide reaction product with multifunctional acrylate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Acetoacetanilide reaction product with... New Uses for Specific Chemical Substances § 721.10390 Acetoacetanilide reaction product with... chemical substance identified generically as acetoacetanilide reaction product with...

  3. 40 CFR 721.8085 - Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of substituted... Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated (generic). (a... generically as reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

  4. 40 CFR 721.10154 - Quaternary ammonium compounds, dicoco alkyldimethyl, chlorides, reaction products with silica.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... alkyldimethyl, chlorides, reaction products with silica. 721.10154 Section 721.10154 Protection of Environment..., dicoco alkyldimethyl, chlorides, reaction products with silica. (a) Chemical substance and significant..., dicoco alkyldimethyl, chlorides, reaction products with silica (PMN P-08-157; CAS No. 956147-76-5)...

  5. Scaling in situ cosmogenic nuclide production rates using analytical approximations to atmospheric cosmic-ray fluxes

    NASA Astrophysics Data System (ADS)

    Lifton, Nathaniel; Sato, Tatsuhiko; Dunai, Tibor J.

    2014-01-01

    Several models have been proposed for scaling in situ cosmogenic nuclide production rates from the relatively few sites where they have been measured to other sites of interest. Two main types of models are recognized: (1) those based on data from nuclear disintegrations in photographic emulsions combined with various neutron detectors, and (2) those based largely on neutron monitor data. However, stubborn discrepancies between these model types have led to frequent confusion when calculating surface exposure ages from production rates derived from the models. To help resolve these discrepancies and identify the sources of potential biases in each model, we have developed a new scaling model based on analytical approximations to modeled fluxes of the main atmospheric cosmic-ray particles responsible for in situ cosmogenic nuclide production. Both the analytical formulations and the Monte Carlo model fluxes on which they are based agree well with measured atmospheric fluxes of neutrons, protons, and muons, indicating they can serve as a robust estimate of the atmospheric cosmic-ray flux based on first principles. We are also using updated records for quantifying temporal and spatial variability in geomagnetic and solar modulation effects on the fluxes. A key advantage of this new model (herein termed LSD) over previous Monte Carlo models of cosmogenic nuclide production is that it allows for faster estimation of scaling factors based on time-varying geomagnetic and solar inputs. Comparing scaling predictions derived from the LSD model with those of previously published models suggest potential sources of bias in the latter can be largely attributed to two factors: different energy responses of the secondary neutron detectors used in developing the models, and different geomagnetic parameterizations. Given that the LSD model generates flux spectra for each cosmic-ray particle of interest, it is also relatively straightforward to generate nuclide-specific scaling

  6. Evaluation of a detailed gas-phase atmospheric reaction mechanism using environmental chamber data

    NASA Astrophysics Data System (ADS)

    Carter, William P. L.; Lurmann, Fredrick W.

    This paper describes an evaluation of the performance of a detailed gas-phase reaction mechanism in simulating the results of 561 experiments carried out in four different environmental chambers. The experiments included background air, NO x-air, CONO x-air and aldehyde-air irradiations used for chamber characterization, NO x-air irradiations of single organics as well as simple and complex organic mixtures, and irradiations of auto exhaust. The methods used to represent the major chamber effects and the lighting characteristics in the model simulations of the experiments are described and their associated uncertainties are discussed. Statistical measures of the performance of the mechanism in simulating results of the various types of experiments are summarized and discussed. The mechanism was able to predict maximum ozone yields and rates of NO oxidation to within ±30% for 63% of the experiments modeled, and to within ±50% for 85% of the runs. There is a slight bias (˜15%) towards overprediction of ozone in mixture runs. Although there are cases where the simulations suggest possible problems with the gas-phase mechanism, much of the variability in the goodness of the fits could be attributed to uncertainties in chamber effects. It is concluded that better characterization of chamber conditions are needed if more comprehensive tests of atmospheric photochemical mechanisms are desired.

  7. Atmospheric leakage and condensate production in NASA's biomass production chamber. Effect of diurnal temperature cycles

    NASA Technical Reports Server (NTRS)

    Wheeler, Raymond M.; Drese, John H.; Sager, John C.

    1991-01-01

    A series of tests were conducted to monitor atmospheric leakage rate and condensate production in NASA's Biomass Production Chamber (BPC). Water was circulated through the 64 plant culture trays inside the chamber during the tests but no plants were present. Environmental conditions were set to a 12-hr photoperiod with either a matching 26 C (light)/20 C (dark) thermoperiod, or a constant 23 C temperature. Leakage, as determined by carbon dioxide decay rates, averaged about 9.8 percent for the 26 C/20 C regime and 7.3 percent for the constant 23 C regime. Increasing the temperature from 20 C to 26 C caused a temporary increase in pressure (up to 0.5 kPa) relative to ambient, while decreasing the temperature caused a temporary decrease in pressure of similar magnitude. Little pressure change was observed during transition between 23 C (light) and 23 C (dark). The lack of large pressure events under isothermal conditions may explain the lower leakage rate observed. When only the plant support inserts were placed in the culture trays, condensate production averaged about 37 liters per day. Placing acrylic germination covers over the tops of culture trays reduced condensate production to about 7 liters per day. During both tests, condensate production from the lower air handling system was 60 to 70 percent greater than from the upper system, suggesting imbalances exist in chilled and hot water flows for the two air handling systems. Results indicate that atmospheric leakage rates are sufficiently low to measure CO2 exchange rates by plants and the accumulation of certain volatile contaminants (e.g., ethylene). Control system changes are recommended in order to balance operational differences (e.g., humidity and temperature) between the two halves of the chamber.

  8. Mass identification of the neutral products generated in the plasma treatment of polluted atmospheres

    NASA Astrophysics Data System (ADS)

    Seymour, David

    2013-09-01

    Plasmas produced using Dielectric Barrier Discharge (DBD) devices are very effective in the abatement of air pollution resulting from, for example, the emission of volatile organic compounds (VCOs) by a range of industrial and agricultural processes. The development and monitoring of effective DBD systems can be investigated by advanced mass spectrometric methods specifically configured for analysis at high and atmospheric pressures The present work involves the operation of a small DBD reactor which uses either a helium or nitrogen carrier gas to sustain the plasma to which may be added reactive gases, such as oxygen, as well as samples of pollutants such as chlorinated hydrocarbons, including trichloroethylene. The mass spectrometric analysis was performed using a specially configured system manufactured by Hiden Analytical Ltd. The DBD source may also be combined with a catalyst for plasma-enhanced catalysis. The neutral products of the reactions proceeding in the plasma at atmospheric pressure are sampled through the capillary sampling system which also reduces the pressure of the gas mixture delivered to the ionisation source of the quadrupole mass spectrometer. The ions produced are subsequently mass identified. We describe typical data and comment on the advantages of this technique.

  9. Production of gamma rays with energies greater than 30 MeV in the atmosphere

    NASA Technical Reports Server (NTRS)

    Thompson, D.; Fichtel, C.; Kniffen, D.

    1974-01-01

    A three-dimensional study of atmospheric gamma rays with energy greater than 30 MeV has been carried out. Experimental results were obtained from four balloon flights from Palestine, Texas, with a 15 cm by 15 cm digitized wire grid spark chamber. The energy spectrum for downward-moving gamma rays steepens with increasing atmospheric depth. Near the top of the atmosphere, the spectrum steepens with increasing zenith angle. Experimental results compare reasonably well with a three-dimensional Monte Carlo calculation of atmospheric gamma ray production. Inclusion of upward-moving gamma rays makes possible the use of atmospheric secondaries for in-flight calibration of satellite gamma ray detectors.

  10. A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.

    PubMed

    Gallis, Michael A; Bond, Ryan B; Torczynski, John R

    2009-09-28

    Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.

  11. Chlorination of parabens: reaction kinetics and transformation product identification.

    PubMed

    Mao, Qianhui; Ji, Feng; Wang, Wei; Wang, Qiquan; Hu, Zhenhu; Yuan, Shoujun

    2016-11-01

    The reactivity and fate of parabens during chlorination were investigated in this work. Chlorination kinetics of methylparaben (MeP), ethylparaben (EtP), propylparaben (PrP), and butylparaben (BuP) were studied in the pH range of 4.0 to 11.0 at 25 ± 1 °C. Apparent rate constants (k app) of 9.65 × 10(-3) M(-0.614)·s(-1), 1.77 × 10(-2) M(-1.019)·s(-1), 2.98 × 10(-2) M(-0.851)·s(-1), and 1.76 × 10(-2) M(-0.860)·s(-1) for MeP, EtP, PrP, and BuP, respectively, were obtained at pH 7.0. The rate constants depended on the solution pH, temperature, and NH4(+) concentration. The maximum k app was obtained at pH 8.0, and the minimum value was obtained at pH 11.0. The reaction rate constants increased with increasing temperature. When NH4(+) was added to the solution, the reaction of parabens was inhibited due to the rapid formation of chloramines. Two main transformation products, 3-chloro-parabens and 3,5-dichloro-parabens, were identified by GC-MS and LCMS-IT-TOF, and a reaction pathway was proposed. Dichlorinated parabens accumulated in solution, which is a threat to human health and the aqueous environment.

  12. Mechanism and kinetics of the reaction of 1,4-thioxane with O3 in the atmosphere - A theoretical study

    NASA Astrophysics Data System (ADS)

    Sandhiya, L.; Kolandaivel, P.; Senthilkumar, K.

    2012-02-01

    A theoretical investigation of the atmospheric oxidation of a cyclic organosulfur compound 1,4-thioxane by O3 is performed. The pathways for the reaction of 1,4-thioxane with O3 have been modeled using B3LYP, M06-2X, MPW1K and MP2 level of theories with 6-31G(d,p), 6-311G(d,p) and 6-31+G(d,p) basis sets. The reaction is initiated by the formation of a primary ozonide, followed by a biradical, which on subsequent reactions with other atmospheric species produces hydroxyl radical, hydrogen peroxides and organic peroxides. The results obtained from DFT calculations were subsequently used to perform canonical variational transition-state theory calculations to determine the rate constant. The calculated rate constant is in good agreement with the available experimental data.

  13. Maillard reaction products as antimicrobial components for packaging films.

    PubMed

    Hauser, Carolin; Müller, Ulla; Sauer, Tanja; Augner, Kerstin; Pischetsrieder, Monika

    2014-02-15

    Active packaging foils with incorporated antimicrobial agents release the active ingredient during food storage. Maillard reaction products (MRPs) show antimicrobial activity that is at least partially mediated by H2O2. De novo generation of H2O2 by an MRP fraction, extracted from a ribose/lysine Maillard reaction mixture by 85% ethanol, was monitored at three concentrations (1.6, 16.1, and 32.3g/L) and three temperatures (4, 25, and 37 °C) between 0 and 96 h, reaching a maximum of 335 μM H2O2 (32.3g/L, 37 °C, 96 h). The active MRP fraction (16.1g/L) completely inhibited the growth of Escherichia coli for 24h and was therefore incorporated in a polyvinyl acetate-based lacquer and dispersed onto a low-density polyethylene film. The coated film generated about 100 μM H2O2 and resulted in a log-reduction of >5 log-cycles against E. coli. Thus, MRPs can be considered as active ingredients for antimicrobial packaging materials.

  14. Rapid electrochemiluminescence assays of polymerase chain reaction products.

    PubMed

    Kenten, J H; Casadei, J; Link, J; Lupold, S; Willey, J; Powell, M; Rees, A; Massey, R

    1991-09-01

    We demonstrate the first use of an electrochemiluminescent (ECL) label, [4-(N-succimidyloxycarbonylpropyl)-4'-methyl-2,2'- bipyridine]ruthenium(II) dihexafluorophosphate (Origen label; IGEN Inc.), in DNA probe assays. This label allows rapid (less than 25 min) quantification and detection of polymerase chain reaction (PCR)-amplified products from oncogenes, viruses, and cloned genes. For the PCR, we used labeled oligonucleotide primers complementary to human papiloma virus and the Ha-ras oncogene. These samples were followed by ECL analysis or hybridization with specific, Origen-labeled oligonucleotide probes. These studies demonstrate the speed, specificity, and effectiveness of the new ECL labels, compared with 32P, for nucleic acid probe applications. We describe formats involving conventional methodologies and a new format that requires no wash step, allowing simple and rapid sample analysis. These rapid assays also reduce PCR contamination, by requiring less sample handling. Improvements in ECL detectability are currently under investigation for use in DNA probe assays without amplification.

  15. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces.

    PubMed

    Chapleski, Robert C; Zhang, Yafen; Troya, Diego; Morris, John R

    2016-07-07

    Heterogeneous chemistry of the most important atmospheric oxidants, O3, NO3, and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O3, NO3, and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, researchers are developing an understanding for how surface structure and functionality affect interfacial chemistry with this class of highly oxidizing pollutants. Together with future research initiatives, these studies will provide a more complete description of atmospheric chemistry and help others more accurately predict the properties of aerosols, the environmental impact of interfacial oxidation, and the concentrations of tropospheric gases.

  16. Sorption enhanced reaction process (SERP) for the production of hydrogen

    SciTech Connect

    Hufton, J.; Mayorga, S.; Gaffney, T.; Nataraj, S.; Rao, M.; Sircar, S.

    1998-08-01

    The novel Sorption Enhanced Reaction Process has the potential to decrease the cost of hydrogen production by steam methane reforming. Current effort for development of this technology has focused on adsorbent development, experimental process concept testing, and process development and design. A preferred CO{sub 2} adsorbent, K{sub 2}CO{sub 3} promoted hydrotalcite, satisfies all of the performance targets and it has been scaled up for process testing. A separate class of adsorbents has been identified which could potentially improve the performance of the H{sub 2}-SER process. Although this material exhibits improved CO{sub 2} adsorption capacity compared to the HTC adsorbent, its hydrothermal stability must be improved. Single-step process experiments (not cyclic) indicate that the H{sub 2}-SER reactor performance during the reaction step improves with decreasing pressure and increasing temperature and steam to methane ratio in the feed. Methane conversion in the H{sub 2}-SER reactor is higher than for a conventional catalyst-only reactor operated at similar temperature and pressure. The reactor effluent gas consists of 90+% H{sub 2}, balance CH{sub 4}, with only trace levels (< 50 ppm) of carbon oxides. A best-case process design (2.5 MMSCFD of 99.9+% H{sub 2}) based on the HTC adsorbent properties and a revised SER process cycle has been generated. Economic analysis of this design indicates the process has the potential to reduce the H{sub 2} product cost by 25--31% compared to conventional steam methane reforming.

  17. Production of hydrogen peroxide and organic peroxides in the gas phase reactions of ozone with natural alkenes

    NASA Astrophysics Data System (ADS)

    Simonaitis, R.; Olszyna, K. J.; Meagher, J. F.

    The formation of H2O2 and organic peroxides in the reaction of O3 with trans-2-butene and naturally occurring alkenes has been studied using a 31 m3 reaction chamber. H2O2 and organic peroxides were found to be products of the O3 reaction with trans-2-butene, isoprene, α and ß-pinene, and limonene. Water is necessary for the formation of H2O2 and most of the H2O2 is formed via a route that does not involve HO2 radicals. Our results indicate that the reaction of O3 with natural alkenes may be a significant source of atmospheric H2O2, particularly in forest and rural areas.

  18. Production of hydrogen peroxide and organic peroxides in the gas phase reactions of ozone with natural alkenes

    SciTech Connect

    Simonaitis, R.; Olszyna, K.J.; Meagher, J.F.

    1991-01-01

    The formation of H{sub 2}O{sub 2} and organic peroxides in the reaction of O{sub 3} with trans-2-butene and naturally occurring alkenes has been studied using a 31 m{sup 3} reaction chamber. H{sub 2}O{sub 2} and organic peroxides were found to be products of the O{sub 3} reaction with trans-2-butene, isoprene, {alpha} and {beta}-pinene, and limonene. Water is necessary for the formation of H{sub 2}O{sub 2} and most of the H{sub 2}O{sub 2} is formed via a route that does not involve HO{sub 2} radicals. These results indicate that the reaction of O{sub 3} with natural alkenes may be a significant source of atmospheric H{sub 2}O{sub 2}, particularly in forest and rural areas.

  19. Observation of a new channel, the production of CH3, in the abstraction reaction of OH radicals with acetaldehyde.

    PubMed

    Howes, Neil U M; Lockhart, James P A; Blitz, Mark A; Carr, Scott A; Baeza-Romero, Maria Teresa; Heard, Dwayne E; Shannon, Robin J; Seakins, Paul W; Varga, T

    2016-09-29

    Using laser flash photolysis coupled to photo-ionization time-of-flight mass spectrometry (PIMS), methyl radicals (CH3) have been detected as primary products from the reaction of OH radicals with acetaldehyde (ethanal, CH3CHO) with a yield of ∼15% at 1-2 Torr of helium bath gas. Supporting measurements based on laser induced fluorescence studies of OH recycling in the OH/CH3CHO/O2 system are consistent with the PIMS study. Master equation calculations suggest that the origin of the methyl radicals is from prompt dissociation of chemically activated acetyl products and hence is consistent with previous studies which have shown that abstraction, rather than addition/elimination, is the sole route for the OH + acetaldehyde reaction. However, the observation of a significant methyl product yield suggests that energy partitioning in the reaction is different from the typical early barrier mechanism where reaction exothermicity is channeled preferentially into the newly formed bond. The master equation calculations predict atmospheric yields of methyl radicals of ∼9%. The implications of the observations in atmospheric and combustion chemistry are briefly discussed.

  20. Sorption Enhanced Reaction Process (SERP) for production of hydrogen

    SciTech Connect

    Anand, M.; Hufton, J.; Mayorga, S.

    1996-10-01

    Sorption Enhanced Reaction Process (SERP) is a novel process that is being developed for the production of lower cost hydrogen by steam-methane reforming (SMR). In this process the reaction of methane with steam is carried out in the presence of an admixture of a catalyst and a selective adsorbent for carbon dioxide. The key consequences of SERP are: (i) reformation reaction is carried out at a significantly lower temperature (300-500{degrees}C) than that in a conventional SMR reactor (800-1100{degrees}C), while achieving the same conversion of methane to hydrogen, (ii) the product hydrogen is obtained at reactor pressure (200-400 psig) and at 98+% purity directly from the reactor (compared to only 70-75% H{sub 2} from conventional SMR reactor), (iii) downstream hydrogen purification step is either eliminated or significantly reduced in size. The first phase of the program has focused on the development of a sorbent for CO{sub 2} which has (a) reversible CO{sub 2} capacity >0.3 mmol/g at low partial pressures of CO{sub 2} (0.1 - 1.0 atm) in the presence of excess steam (pH{sub 2}O/pCO{sub 2}>20) at 400-500{degrees}C and (b) fast sorption-desorption kinetics for CO{sub 2}, at 400-500{degrees}C. Several families of supported sorbents have been identified that meet the target CO{sub 2} capacity. A few of these sorbents have been tested under repeated sorption/desorption cycles and extended exposure to high pressure steam at 400-500{degrees}C. One sorbent has been scaled up to larger quantities (2-3 kg) and tested in the laboratory process equipment for sorption and desorption kinetics of CO{sub 2}. The CO{sub 2}, sorption and desorption kinetics are desirably fast. This was a critical path item for the first phase of the program and now has been successfully demonstrated. A reactor has been designed that will allow nearly isothermal operation for SERP-SMR. This reactor was integrated into an overall process flow diagram for the SERP-SMR process.

  1. ELECTRON-DRIVEN REACTIONS IN PROTO-PLANETARY ATMOSPHERES: METASTABLE ANIONS OF GASEOUS o-BENZYNE

    SciTech Connect

    Carelli, F.; Sebastianelli, F.; Baccarelli, I.; Gianturco, F. A.

    2010-03-20

    In this paper, we present an investigation into low-energy electron scattering (E < 15 eV) processes from a specific benzene-like polyatomic target such as ortho-benzyne, o-C{sub 6}H{sub 4}({sup 1}SIGMA), in order to gain a better understanding of the effects that possible low-lying metastable electron-attachment states could have on its nuclear fragmentation dynamics. The current importance of the dynamical evolution of this molecule lies in the fact that o-C{sub 6}H{sub 4} is considered to be relevant for the circumstellar synthesis of large polycyclic aromatic hydrocarbons (PAHs), as a precursor for C{sub 6}H{sub 6} production via ion-based ring closure reaction from C{sub 2}H{sub 2}. Our parameter-free scattering calculations are performed within the molecular reference frame, where we obtain the metastable anionic states for the nuclear equilibrium configuration and further characterize the properties of such transient anions with respect to those found earlier for the benzene molecule. Our quantum studies indicate that o-C{sub 6}H{sub 4} is a more efficient producer of compact, fairly long-lived anionic intermediates than benzene itself; hence, this should more rapidly enter the chemical reaction cycles of PAHs formation, thereby disappearing from possible direct observation as a stable anion.

  2. Gas phase reaction of OH radicals with ( E)-β-farnesene at 296 ± 2 K: Rate coefficient and carbonyl products

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan; Bejan, Iustinian; Sodeau, John R.; Wenger, John C.

    2012-01-01

    The gas phase reaction of OH radicals with ( E)-β-farnesene was investigated in a 3.91 m 3 atmospheric simulation chamber at 296 ± 2 K and atmospheric pressure. The relative rate method was used to determine the reaction rate coefficient of (1.71 ± 0.21) × 10 -10 cm 3 molecule -1 s -1. Gas phase carbonyl products were collected using a denuder sampling technique and analyzed with GC/MS following derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA). The reaction products detected were acetone, 4-oxopentanal, 4-methylenehex-5-enal, 6-methylhept-5-en-2-one and ( E)-4-methyl-8-methylenedeca-4,9-dienal. A minor reaction product with MW 112 was tentatively identified as 4-oxohex-5-enal or 2-methylenepentanedial. A mechanism for the OH radical-initiated oxidation of ( E)-β-farnesene is proposed, which accounts for all of the products observed in this study. The results of this work indicate that the atmospheric reaction of ( E)-β-farnesene with OH radicals has a lifetime of around 1 h and is a potential source of the ubiquitous carbonyls, acetone, 4-oxopentanal and 6-methylhept-5-en-2-one in the atmosphere.

  3. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  4. OH Production from Reactions of Organic Peroxy Radicals with HO2 : Recent Studies on Ether-Derived Peroxy Radicals

    NASA Astrophysics Data System (ADS)

    Orlando, J. J.; Tyndall, G. S.; Kegley Owen, C. S.; Reynoldson, N.

    2013-12-01

    There is now ample evidence supporting significant formation of OH radicals in the reaction of HO2 with certain organic peroxy radicals (RO2). These reaction channels serve to promote radical propagation, and thus have the potential to alter HOx budgets and partitioning and hence tropospheric oxidative capacity. While much focus has been placed on OH production from reactions involving carbonyl-containing RO2 species, it is also the case that other oxygen- substituted peroxy species (e.g., CH3OCH2OO, HOCH2OO) likely generate OH in their reactions with HO2 (see ref. 1 and refs therein). In this work, the Cl-atom-initiated oxidation of two ethers, diethyl and diisopropyl ether, is investigated over ranges of conditions in an environmental chamber, using both FTIR and GC-FID methods for product quantification. Preliminary analysis suggests that significant OH production is occurring in the reaction of HO2 with CH3CH2OCH(OO)CH3, and also provides evidence for a rapid unimolecular reaction of diisopropyl ether-derived peroxy radicals. Details of these and other results will be described. 1. Orlando, J. J., and G. S. Tyndall, 2012: Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance, Chemical Society Reviews, 41, 6294-6317, doi: 10.1039/C2CS35166H.

  5. Kinetics of the unimolecular reaction of CH2OO and the bimolecular reactions with the water monomer, acetaldehyde and acetone under atmospheric conditions.

    PubMed

    Berndt, Torsten; Kaethner, Ralf; Voigtländer, Jens; Stratmann, Frank; Pfeifle, Mark; Reichle, Patrick; Sipilä, Mikko; Kulmala, Markku; Olzmann, Matthias

    2015-08-14

    Stabilized Criegee Intermediates (sCIs) have been identified as oxidants of atmospheric trace gases such as SO2, NO2, carboxylic acids or carbonyls. The atmospheric sCI concentrations, and accordingly their importance for trace gas oxidation, are controlled by the rate of the most important loss processes, very likely the unimolecular reactions and the reaction with water vapour (monomer and dimer) ubiquitously present at high concentrations in the troposphere. In this study, the rate coefficients of the unimolecular reaction of the simplest sCI, formaldehyde oxide, CH2OO, and its bimolecular reaction with the water monomer have been experimentally determined at T = (297 ± 1) K and at atmospheric pressure by using a free-jet flow system. CH2OO was produced by the reaction of ozone with C2H4, and CH2OO concentrations were probed indirectly by detecting H2SO4 after titration with SO2. Time-resolved experiments yield a rate coefficient of the unimolecular reaction of k(uni) = (0.19 ± 0.07) s(-1), a value that is supported by quantum-chemical and statistical rate theory calculations as well as by additional measurements performed under CH2OO steady-state conditions. A rate coefficient of k(CH2OO+H2O) = (3.2 ± 1.2) × 10(-16) cm(3) molecule(-1) s(-1) has been determined for sufficiently low H2O concentrations (<10(15) molecule cm(-3)) that allow separation from the CH2OO reaction with the water dimer. In order to evaluate the accuracy of the experimental approach, the rate coefficients of the reactions with acetaldehyde and acetone were reinvestigated. The obtained rate coefficients k(CH2OO+acetald) = (1.7 ± 0.5) × 10(-12) and k(CH2OO+acetone) = (3.4 ± 0.9) × 10(-13) cm(3) molecule(-1) s(-1) are in good agreement with literature data.

  6. Calculations of long-lived isomer production in neutron reactions

    SciTech Connect

    Chadwick, M.B.; Young, P.G.

    1991-01-01

    We present theoretical calculations for the production of the long-lived isomers: {sup 121m}Sn (11/2-, 55 yr), {sup 166m}Ho(7-, 1200 yr), {sup 184m}Re(8+, 165 d), {sup 186m}Re(8+, 2{times}10{sup 5} yr), {sup 178m}Hf(16+, 31 yr), {sup 179m}Hf(25/2-, 25 d), {sup 192m}Ir(9+, 241 yr), all which pose potential radiation activation problems in nuclear fusion reactors if produced in 14-MeV neutron-induced reactions. We consider mainly (n,2n) production modes, but also (n,n{sup {prime}}) and (n,{gamma}) where necessary, and compare our results both with experimental data (where available) and systematics. We also investigate the dependence of the isomeric cross section ratio on incident neutron energy for the isomers under consideration. The statistical Hauser-Feshbach plus preequilibrium code GNASH was used for the calculations. Where discrete state experimental information was lacking, rotational band members above the isomeric state, which can be justified theoretically but have not been experimentally resolved, were reconstructed. 16 refs., 9 figs., 6 tabs.

  7. A Review of Microwave-Assisted Reactions for Biodiesel Production.

    PubMed

    Nomanbhay, Saifuddin; Ong, Mei Yin

    2017-06-15

    The conversion of biomass into chemicals and biofuels is an active research area as trends move to replace fossil fuels with renewable resources due to society's increased concern towards sustainability. In this context, microwave processing has emerged as a tool in organic synthesis and plays an important role in developing a more sustainable world. Integration of processing methods with microwave irradiation has resulted in a great reduction in the time required for many processes, while the reaction efficiencies have been increased markedly. Microwave processing produces a higher yield with a cleaner profile in comparison to other methods. The microwave processing is reported to be a better heating method than the conventional methods due to its unique thermal and non-thermal effects. This paper provides an insight into the theoretical aspects of microwave irradiation practices and highlights the importance of microwave processing. The potential of the microwave technology to accomplish superior outcomes over the conventional methods in biodiesel production is presented. A green process for biodiesel production using a non-catalytic method is still new and very costly because of the supercritical condition requirement. Hence, non-catalytic biodiesel conversion under ambient pressure using microwave technology must be developed, as the energy utilization for microwave-based biodiesel synthesis is reported to be lower and cost-effective.

  8. A Review of Microwave-Assisted Reactions for Biodiesel Production

    PubMed Central

    Nomanbhay, Saifuddin; Ong, Mei Yin

    2017-01-01

    The conversion of biomass into chemicals and biofuels is an active research area as trends move to replace fossil fuels with renewable resources due to society’s increased concern towards sustainability. In this context, microwave processing has emerged as a tool in organic synthesis and plays an important role in developing a more sustainable world. Integration of processing methods with microwave irradiation has resulted in a great reduction in the time required for many processes, while the reaction efficiencies have been increased markedly. Microwave processing produces a higher yield with a cleaner profile in comparison to other methods. The microwave processing is reported to be a better heating method than the conventional methods due to its unique thermal and non-thermal effects. This paper provides an insight into the theoretical aspects of microwave irradiation practices and highlights the importance of microwave processing. The potential of the microwave technology to accomplish superior outcomes over the conventional methods in biodiesel production is presented. A green process for biodiesel production using a non-catalytic method is still new and very costly because of the supercritical condition requirement. Hence, non-catalytic biodiesel conversion under ambient pressure using microwave technology must be developed, as the energy utilization for microwave-based biodiesel synthesis is reported to be lower and cost-effective. PMID:28952536

  9. Kinetic and Product Studies of the Reaction Between Oxidized Mercury Species and Selected Thiols

    NASA Astrophysics Data System (ADS)

    Si, L.; Ariya, P.

    2008-12-01

    Mercury is a global pollutant with severe potential toxicity. The reduction of oxidized mercury species (Hg(II)) to elemental mercury (Hg(0)) affects the global distribution of mercury and competes for methylation processes of mercury in aquatic environment. This study focused on the reduction of Hg(II) by several selected thiols using a suite of complementary mass spectrometry and cold vapor fluorescence spectroscopy (CVAFS). Previous studies showed that irradiation of benzene solution of six mercury dimercaptides (benzyl, n-propyl, isopropyl, cyclopentyl, t-butyl and phenyl sulfide) at part-per-million level by a mercury arc lamp under a nitrogen atmosphere caused the formation of Hg(0) to occur. The reaction kinetics was studied using CVAFS, and the products of the reaction were analyzed using Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass spectrometry (MALDI-TOF-MS) and Gas Chromatography-Mass spectrometry (GC-MS). The kinetic data were obtained for 1-butanethiol, and 1-pentanethiol, 1-hexanethiol at environmental relevant conditions. The effects of light, pH, dissolved oxygen and chloride ion on reaction rates were also investigated. We will present our results and discuss their potential environmental implications on mercury cycling.

  10. Temperature Dependence of the Rate Constant for the CH3 Recombination Reaction: A Loss Process in Outer Planet Atmospheres

    NASA Technical Reports Server (NTRS)

    Cody, R. J.; Payne, W. A.; Thorn, R. P., Jr.; Romani, P. N.; Stief, L. J.; Nesbitt, F. L.; Iannone, M. A.; Tardy, D. C.

    2002-01-01

    The methyl free radical (CH3) has been observed in the atmospheres of Saturn and Neptune by the ISO satellite. There are discrepancies between the column densities for the CH3 radical derived from the ISO observations and the column densities derived from atmospheric photochemical models. For Neptune the model column density is 1.5 times that derived from ISO. For Saturn the model is 6 times that from ISO. The recombination of methyl radicals is the major loss process for methyl in these atmospheres. The serious disagreement between observed and calculated levels of CH3 has led to suggestions that the atmospheric models greatly underestimated the loss of CH3 due to poor knowledge of the rate of the reaction (1) CH3 + CH3 + M goes to C2H6 + M at the low temperatures and pressures of these atmospheric systems. Although the reaction CH3 + CH3 + M goes to C2H6 + M has been extensively studied both theoretically and experimentally, the laboratory conditions have been, with only a few exceptions, higher temperatures (T greater than 298K), higher pressures (P greater than or equal to 10 Torr - 13.3 mbar) or M=Ar rather than H2 or He as the bath gas.

  11. Red clouds in reducing atmospheres. [polymer production by UV irradiation in planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Khare, B. N.; Sagan, C.

    1973-01-01

    A dark reddish-brown high-molecular weight polymer is produced by long wavelength ultraviolet irradiation of abundant gases in reducing planetary atmospheres. The polymer is examined by paper chromatography, mass spectrometry, and infrared, visible, and ultraviolet spectroscopy. High carbon-number straight-chain alkanes with NH2 and, probably, OH and C = O groups are identified, along with amino acids. There are chemical similarities between this polymer and organic compounds recovered from carbonaceous chondrites and precambrian sediments. The visible and near-ultraviolet transmission spectrum of the polymer shows its absorption optical depth to be redder than lambda(-2) and perhaps similar in coloration to the clouds of Jupiter, Saturn, and Titan. The nitrile content is small, and the polymer should be semitransparent in the 5 micrometer atmospheric window. Such polymers may be a common constituent of clouds in the outer solar system and on the early earth.

  12. Termolecular ion-molecule reactions in Titan's atmosphere. IV. A search made at up to 1 micron in pure hydrocarbons.

    PubMed

    Anicich, Vincent G; Wilson, Paul; McEwan, Murray J

    2003-08-01

    The results of a study of ion-molecule reactions occurring in pure methane, acetylene, ethylene, ethane, propyne, propene, propane, and diacetylene at pressures up to 40 microns of pressure are reported. A variety of experimental methods are used: The standard double resonance in an ICR, for determination of the precursor ions and the modulated double resonance ejection in an ICR, for the determination of the daughter ions. The FA-SIFT technique was used for validation and examination of termolecular reactions with rate coefficients that are less than 10(-26) cm(6) s(-1). An extensive database of reaction kinetics already exists for many of these reactions. The main point of this study was the determination of the accuracy of this database and to search for any missing reactions and reaction channels that may have been omitted from earlier investigations. A specific objective of this work was to extend the study to the highest pressures possible to find out if there were any important termolecular reaction channels occurring. A new approach was used here. In the pure hydrocarbon gases the mass spectra were followed as a function of the pressure changes of the gas. An initial guess was first made using the current literature as a source of the reaction kinetics that were expected. A model of the ion abundances was produced from the solution of the partial differential equations in terms of reaction rate coefficients and initial abundances. The experimental data was fitted to the model for all of the pressures by a least squares minimization to the reaction rate coefficients and initial abundances. The reaction rate coefficients obtained from the model were then compared to the literature values. Several new channels and reactions were discovered when the modeled fits were compared to the actual data. This is all explained in the text and the implications of these results are discussed for the Titan atmosphere.

  13. Termolecular ion-molecule reactions in Titan's atmosphere. IV. A search made at up to 1 micron in pure hydrocarbons

    NASA Technical Reports Server (NTRS)

    Anicich, Vincent G.; Wilson, Paul; McEwan, Murray J.

    2003-01-01

    The results of a study of ion-molecule reactions occurring in pure methane, acetylene, ethylene, ethane, propyne, propene, propane, and diacetylene at pressures up to 40 microns of pressure are reported. A variety of experimental methods are used: The standard double resonance in an ICR, for determination of the precursor ions and the modulated double resonance ejection in an ICR, for the determination of the daughter ions. The FA-SIFT technique was used for validation and examination of termolecular reactions with rate coefficients that are less than 10(-26) cm(6) s(-1). An extensive database of reaction kinetics already exists for many of these reactions. The main point of this study was the determination of the accuracy of this database and to search for any missing reactions and reaction channels that may have been omitted from earlier investigations. A specific objective of this work was to extend the study to the highest pressures possible to find out if there were any important termolecular reaction channels occurring. A new approach was used here. In the pure hydrocarbon gases the mass spectra were followed as a function of the pressure changes of the gas. An initial guess was first made using the current literature as a source of the reaction kinetics that were expected. A model of the ion abundances was produced from the solution of the partial differential equations in terms of reaction rate coefficients and initial abundances. The experimental data was fitted to the model for all of the pressures by a least squares minimization to the reaction rate coefficients and initial abundances. The reaction rate coefficients obtained from the model were then compared to the literature values. Several new channels and reactions were discovered when the modeled fits were compared to the actual data. This is all explained in the text and the implications of these results are discussed for the Titan atmosphere.

  14. A theoretical study of the mechanism of the atmospherically relevant reaction of chlorine atoms with methyl nitrate, and calculation of the reaction rate coefficients at temperatures relevant to the troposphere.

    PubMed

    Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

    2015-03-21

    The reaction between atomic chlorine (Cl) and methyl nitrate (CH3ONO2) is significant in the atmosphere, as Cl is a key oxidant, especially in the marine boundary layer, and alkyl nitrates are important nitrogen-containing organic compounds, which are temporary reservoirs of the reactive nitrogen oxides NO, NO2 and NO3 (NOx). Four reaction channels HCl + CH2ONO2, CH3OCl + NO2, CH3Cl + NO3 and CH3O + ClNO2 were considered. The major channel is found to be the H abstraction channel, to give the products HCl + CH2ONO2. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/6-31+G** level, while relative electronic energies were improved to the UCCSD(T*)-F12/CBS level. The reaction barrier (ΔE(‡)0K) and reaction enthalpy (ΔH(RX)298K) of the H abstraction channel were computed to be 0.61 and -2.30 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS//M06-2X/6-31+G** level. Reaction barriers (ΔE(‡)0K) for the other channels are more positive and these pathways do not contribute to the overall reaction rate coefficient in the temperature range considered (200-400 K). Rate coefficients were calculated for the H-abstraction channel at various levels of variational transition state theory (VTST) including tunnelling. Recommended ICVT/SCT rate coefficients in the temperature range 200-400 K are presented for the first time for this reaction. The values obtained in the 200-300 K region are particularly important as they will be valuable for atmospheric modelling calculations involving reactions with methyl nitrate. The implications of the results to atmospheric chemistry are discussed. Also, the enthalpies of formation, ΔHf,298K, of CH3ONO2 and CH2ONO2 were computed to be -29.7 and 19.3 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS level.

  15. Quasielastic production of polarized hyperons in antineutrino-nucleon reactions

    NASA Astrophysics Data System (ADS)

    Akbar, F.; Alam, M. Rafi; Athar, M. Sajjad; Singh, S. K.

    2016-12-01

    We have studied the differential cross section as well as the longitudinal and perpendicular components of polarization of the final hyperon (Λ ,Σ ) produced in the antineutrino induced quasielastic charged current reactions on nucleon and nuclear targets. The nucleon-hyperon transition form factors are determined from the experimental data on quasielastic (Δ S =0 ) charged current (anti)neutrino-nucleon scattering and the semileptonic decay of neutron and hyperons assuming G-invariance, T-invariance, and SU(3) symmetry. The vector transition form factors are obtained in terms of nucleon electromagnetic form factors for which various parametrizations available in the literature have been used. A dipole parametrization for the axial vector form factor and the pseudoscalar transition form factor derived in terms of the axial vector form factor assuming PCAC and GT relation extended to the strangeness sector has been used in numerical evaluations. The flux averaged cross section and polarization observables corresponding to the CERN Gargamelle experiment have been calculated for quasielastic hyperon production and found to be in reasonable agreement with the experimental observations. The numerical results for the flux averaged differential cross section d/σ d Q2 and longitudinal (perpendicular) polarization PL(Q2)(PP(Q2)) relevant for the antineutrino fluxes of MINER ν A , MicroBooNE, and T2K experiments have been presented. This will be useful in interpreting future experimental results on production cross sections and polarization observables from the experiments on the quasielastic production of hyperons induced by antineutrinos and exploring the possibility of determining the axial vector and pseudoscalar form factors in the strangeness sector.

  16. Atmospheric reactions between E,E-2,4-hexadienal and OH, NO3 radicals and Cl atoms

    NASA Astrophysics Data System (ADS)

    Colmenar, I.; Martín, P.; Cabañas, B.; Salgado, S.; Martínez, E.

    2014-12-01

    E,E-2,4-Hexadienal is an α,β-unsaturated aldehyde whose presence in the atmosphere can arise from different sources. The rate coefficients for the reaction of this compound with Cl atoms, OH and NO3 radicals and for the photolysis process have been determined at atmospheric pressure and room temperature. A relative method has been developed with a Fourier Transform Infrared spectrometer (FTIR) or Solid Phase Micro Extraction fiber/chromatography-mass spectrometer (SPME/GC-MS) used as sampling/detection techniques. The absolute rate coefficients k (in units of cm3 molecule-1 s-1) obtained for Cl, OH and NO3 were (3.98 ± 0.44) × 10-10, (6.78 ± 0.47) × 10-11 and (1.34 ± 0.56) × 10-12, respectively. An estimation of the rate coefficient for the reaction of E,E-2,4-hexadienal with OH and NO3 radicals and Cl atoms has been carried out using correlations and SAR methods. The SAR substituent factor for the -C(O)H group, [G-(C(O)H)] = 3.58 × 10-3, has been obtained. This group reactivity factor allows the rate coefficients to be estimated for the reaction of unsaturated aldehydes with NO3 radicals. The results of this study confirm that the reaction of unsaturated aldehydes with Cl atoms is very fast and that the structure of the compound has little influence, with the influence of the structure being more marked in the case of the OH radical reaction and relatively large for the NO3 reaction. The results are consistent with a mechanism in which the first stage is addition of an atom or radical to the double bond of E,E-2,4-hexadienal as the main reaction channel and, to a minor extent, the abstraction of aldehydic hydrogen. These are the first data reported for the atmospheric reactions of this compound and this study therefore contributes to the database of rate coefficients for atmospheric reactions.

  17. Chemical Reaction and Flow Modeling in Fullerene and Nanotube Production

    NASA Technical Reports Server (NTRS)

    Scott, Carl D.; Farhat, Samir; Greendyke, Robert B.

    2004-01-01

    The development of processes to produce fullerenes and carbon nanotubes has largely been empirical. Fullerenes were first discovered in the soot produced by laser ablation of graphite [1]and then in the soot of electric arc evaporated carbon. Techniques and conditions for producing larger and larger quantities of fullerenes depended mainly on trial and error empirical variations of these processes, with attempts to scale them up by using larger electrodes and targets and higher power. Various concepts of how fullerenes and carbon nanotubes were formed were put forth, but very little was done based on chemical kinetics of the reactions. This was mainly due to the complex mixture of species and complex nature of conditions in the reactors. Temperatures in the reactors varied from several thousand degrees Kelvin down to near room temperature. There are hundreds of species possible, ranging from atomic carbon to large clusters of carbonaceous soot, and metallic catalyst atoms to metal clusters, to complexes of metals and carbon. Most of the chemical kinetics of the reactions and the thermodynamic properties of clusters and complexes have only been approximated. In addition, flow conditions in the reactors are transient or unsteady, and three dimensional, with steep spatial gradients of temperature and species concentrations. All these factors make computational simulations of reactors very complex and challenging. This article addresses the development of the chemical reaction involved in fullerene production and extends this to production of carbon nanotubes by the laser ablation/oven process and by the electric arc evaporation process. In addition, the high-pressure carbon monoxide (HiPco) process is discussed. The article is in several parts. The first one addresses the thermochemical aspects of modeling; and considers the development of chemical rate equations, estimates of reaction rates, and thermodynamic properties where they are available. The second part

  18. Basics of quantitative polymerase chain reaction: 2. Electrophoresis and quantitation of polymerase chain reaction products.

    PubMed

    Sundfors, C; Collan, Y

    1996-01-01

    The performance of agarose and polyacrylamide (PAGE) gels in quantitating polymerase chain reaction (PCR) amplified c-erbB2 and p53 gene sequences (213 and 133 base pairs, respectively) was studied by applying image analysis on photographed ethidium bromide stained gels. The 5 mm thick agarose gels were more insensitive than the 1 mm thin PAGE gels and already started to show saturation effects within a narrow concentration range. The explanation is the greater dilution of band-associated products within the volume of the gel and the inefficient penetration of exciting UV light through the gel. Such effects produced inconsistency and dramatic variations in the band ratio estimates. In the system used by us, agarose electrophoresis and also electrophoresis using 5 mm thick PAGE gels have only a limited value in quantitation of PCR products with the band density ratios, but both can be used well in qualitative work. The far thinner (1 mm) PAGE gels, which did not markedly absorb UV light, performed better in the light of band density ratio estimates. The linear or approximately linear range of concentrations was wider. The coefficient of variation of band ratio, when estimated from the same gels, after loading them with aliquots of identical DNA from several PCR amplified tubes, was in the range of 4%. The absolute values of band densities had a more remarkable variation (than 4%) in both agarose and PAGE gels. Our recommendation is that quantitation of PCR products be done with band density ratio estimates, and in thin PAGE gels.

  19. Kinetics and mechanism of the atmospheric reactions of atomic chlorine with 1-penten-3-ol and (Z)-2-penten-1-ol: an experimental and theoretical study.

    PubMed

    Rodríguez, Ana; Rodríguez, Diana; Garzón, Andrés; Soto, Amparo; Aranda, Alfonso; Notario, Alberto

    2010-10-14

    Smog chamber/GC techniques were used to investigate the atmospheric degradation of two unsaturated alcohols, 1-penten-3-ol and (Z)-2-penten-1-ol, by oxidation with chlorine atoms at atmospheric pressure of N(2) or air, as a function of temperature. The rate coefficients at 298 K were (units in cm(3) molecule(-1) s(-1)): (2.35 ± 0.31) × 10(-10) and (3.00 ± 0.49) × 10(-10) for 1-penten-3-ol and (Z)-2-penten-1-ol, respectively. The identified and quantified gas-phase products (with molar yields in brackets) were carbonyl compounds such as chloroacetaldehyde (33 ± 1%), propionaldehyde (39 ± 1%), acetaldehyde (8 ± 3%) and 1-penten-3-one (2%) from 1-penten-3-ol; and chlorobutyraldehyde (19 ± 1%), propionaldehyde (27 ± 1%), acetaldehyde (18 ± 2%) and (Z)-2-pentenal (36 ± 1%) from (Z)-2-penten-1-ol. A parallel theoretical study at the QCISD(T)6-311G**//MP2/6-311G** level was carried out to facilitate understanding of the reaction mechanism. Both the theoretical and experimental studies indicated that addition of Cl to the double bond of the unsaturated alcohol is the dominant reaction pathway, although the H-abstraction channel cannot be excluded. The atmospheric lifetimes of those unsaturated alcohols were calculated and the results are discussed.

  20. Impact of Insertion Reaction of O(^1D) Into the Carbonic Acid Molecule in the Atmosphere of Earth and Mars

    NASA Astrophysics Data System (ADS)

    Ghoshal, Sourav; Hazra, Montu K.

    2017-06-01

    In this talk, we present the energetics and kinetics of the insertion reaction of the O(^1D) into the H_2CO_3 molecule that finally produces the percarbonic acid [H_2C(O)O_3] molecule (H_2CO_3 + O(^1D)→ H_2C(O)O_3). The rate constants have been calculated by the Variable-Reaction-Coordinate Variational Transition State Theory (VRC-VTST). From our results, we show that the rate constants of the insertion reaction are significantly higher than the rate constants associated with the H_2O-assisted H_2CO_3 decomposition (H_2CO_3 + H_2O → CO_2 + 2H_2O), acetic acid (AA)-assisted H_2CO_3 decomposition (H_2CO_3 + AA → CO_2 + H_2O + AA) and OH radical-initiated H_2CO_3 degradation reaction (H_2CO_3 + OH^{.} → HCO_3^{.} + H_2O) -which are currently assumed to be the potentially important reaction channels to interpret the atmospheric loss of the H_2CO_3 molecule in the Earth. Finally, we also discuss the potential impact of the H_2O-assisted H_2CO_3 decomposition reaction, OH radical-initiated H_2CO_3 degradation reaction and the above-mentioned insertion reaction on equal footing toward the loss of H_2CO_3 molecule, especially, in the surface of Mars.