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Sample records for acid vapor hno3

  1. Passive sampler for measurements of atmospheric nitric acid vapor (HNO3) concentrations.

    PubMed

    Bytnerowicz, A; Padgett, P E; Arbaugh, M J; Parker, D R; Jones, D P

    2001-12-05

    Nitric acid (HNO3) vapor is an important nitrogenous air pollutant responsible for increasing saturation of forests with nitrogen and direct injury to plants. The USDA Forest Service and University of California researchers have developed a simple and inexpensive passive sampler for monitoring air concentrations of HNO3. Nitric acid is selectively absorbed on 47-mm Nylasorb nylon filters with no interference from particulate NO3-. Concentrations determined with the passive samplers closely corresponded with those measured with the co-located honeycomb annular denuder systems. The PVC protective caps of standardized dimensions protect nylon filters from rain and wind and allow for reliable measurements of ambient HNO3 concentrations. The described samplers have been successfully used in Sequoia National Park, the San Bernardino Mountains, and on Mammoth Mountain in California.

  2. Deposition and adsorption of the air pollutant HNO 3 vapor to soil surfaces

    NASA Astrophysics Data System (ADS)

    Padgett, Pamela E.; Bytnerowicz, Andrzej

    Deposition of nitric acid (HNO 3) vapor to soils has been evaluated in three experimental settings: (1) continuously stirred tank reactors with the pollutant added to clean air, (2) open-top chambers at high ambient levels of pollution with and without filtration reducing particulate nitrate levels, (3) two field sites with high or low pollution loads in the coastal sage plant community of southern California. The results from experiment (1) indicated that the amount of extractable NO 3- from isolated sand, silt and clay fractions increased with atmospheric concentration and duration of exposure. After 32 days, the highest absorption of HNO 3 was determined for clay, followed by silt and sand. While the sand and silt fractions showed a tendency to saturate, the clay samples did not after 32 days of exposure under highly polluted conditions. Absorption of HNO 3 occurred mainly in the top 1 mm layer of the soil samples and the presence of water increased HNO 3 absorption by about 2-fold. Experiment (2) indicated that the presence of coarse particulate NO 3- could effectively block absorption sites of soils for HNO 3 vapor. Experiment (3) showed that soil samples collected from open sites had about 2.5 more extractable NO 3- as compared to samples collected from beneath shrub canopies. The difference in NO 3- occurred only in the upper 1-2 cm as no significant differences in NO 3- concentrations were found in the 2-5 cm soil layers. Extractable NO 3- from surface soils collected from a low-pollution site ranged between 1 and 8 μg NO 3-N g -1, compared to a maximum of 42 μg NO 3-N g -1 for soils collected from a highly polluted site. Highly significant relationship between HNO 3 vapor doses and its accumulation in the upper layers of soils indicates that carefully prepared soil samples (especially clay fraction) may be useful as passive samplers for evaluation of ambient concentrations of HNO 3 vapor.

  3. The effect of nitric acid (HNO3) on growth, spectral, thermal and dielectric properties of triglycine sulphate (TGS) crystal.

    PubMed

    Parimaladevi, R; Sekar, C; Krishnakumar, V

    2010-02-01

    The effect of nitric acid (HNO(3)) addition on the growth of triglycine sulphate (TGS) crystal has been studied from the aqueous solution for various concentrations of nitric acid. Significant changes in the crystal size and morphology have been observed in all the grown samples. Single crystal and powder X-ray diffraction analyses confirm the structure and cell parameter values of pure and HNO(3) doped TGS crystals. FT-Raman and FTIR spectra confirm the characteristics absorption bands of pure and HNO(3) doped TGS crystals. The composition of TGS crystals have been confirmed by CHNS analysis. Physical properties such as thermal, dielectric and mechanical studies have been performed for the pure and HNO(3) doped TGS crystals. The dielectric constants of the crystals have been studied as a function of frequency. The results suggest that the HNO(3) is doped into TGS crystal and that the doping increases its dielectric constant.

  4. Thermochemical Kinetics of H2O and HNO3 on crystalline Nitric Acid Hydrates (alpha-, beta-NAT, NAD) in the range 175-200 K

    NASA Astrophysics Data System (ADS)

    Rossi, Michel J.; Iannarelli, Riccardo

    2015-04-01

    The growth of NAT (Nitric Acid Trihydrate, HNO3x3H2O) and NAD (Nitric Acid Dihydrate, HNO3x2H2O) on an ice substrate, the evaporative lifetime of NAT and NAD as well as the interconversion of alpha- and beta-NAT competing with evaporation and growth under UT/LS conditions depends on the interfacial kinetics of H2O and HNO3 vapor on the condensed phase. Despite the existence of some literature results we have embarked on a systematic investigation of the kinetics using a multidiagnostic experimental approach enabled by the simultaneous observation of both the gas (residual gas mass spectrometry) as well as the condensed phase (FTIR absorption in transmission). We report on thermochemically consistent mass accommodation coefficients alpha and absolute evaporation rates Rev/molecule s-1cm-3 as a function of temperature which yields the corresponding vapor pressures of both H2O and HNO3 in equilibrium with the crystalline phases, hence the term thermochemical kinetics. These results have been obtained using a stirred flow reactor (SFR) using a macroscopic pure ice film of 1 micron or so thickness as a starting substrate mimicking atmospheric ice particles and are reported in a phase diagram specifically addressing UT (Upper Troposphere)/LS (Lower Stratosphere) conditions as far as temperature and partial pressures are concerned. The experiments have been performed either at steady-state flow conditions or in transient supersaturation using a pulsed solenoid valve in order to generate gas pulses whose decay were subsequently monitored in real time. Special attention has been given to the effect of the stainless-steel vessel walls in that Langmuir adsorption isotherms for H2O and HNO3 have been used to correct for wall-adsorption of both probe gases. Typically, the accommodation coefficients of H2O and HNO3 are similar throughout the temperature range whereas the rates of evaporation Rev of H2O are significantly larger than for HNO3 thus leading to the difference in

  5. Dissociation of strong acid revisited: X-ray photoelectron spectroscopy and molecular dynamics simulations of HNO3 in water

    SciTech Connect

    Lewis, Tanza; Winter, Berndt; Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.; Hemminger, J. C.

    2011-08-04

    Molecular-level insight into the dissociation of nitric acid in water is obtained from photoelectron X-ray spectroscopy and first-principles molecular dynamics (MD) simulations. Our combined studies reveal surprisingly abrupt changes in solvation configurations of undissociated nitric acid at approximately 4 M concentration. Experimentally, this is inferred from N1s binding energy shifts of HNO3(aq) as a function of concentration, and is associated with variations in the local electronic structure of the nitrogen atom. It also shows up as a discontinuity in the degree of dissociation as a function of concentration, determined here from the N1s photoelectron signal intensity, which can be separately quantified for undissociated HNO3(aq) and dissociated NO3-(aq). Intermolecular interactions within the nitric acid solution are discussed on the basis of MD simulations, which reveal that molecular HNO3 interacts remarkably weakly with solvating water molecules at low concentration; around 4 M there is a turnover to a more structured solvation shell, accompanied by an increase in hydrogen bonding between HNO3 and water. We suggest that the driving force behind the more structured solvent configuration of HNO3 is the overlap of nitric acid solvent shells that sets in around 4 M concentration. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  6. Dissociation of strong acid revisited: X-ray photoelectron spectroscopy and molecular dynamics simulations of HNO3 in water.

    PubMed

    Lewis, Tanza; Winter, Bernd; Stern, Abraham C; Baer, Marcel D; Mundy, Christopher J; Tobias, Douglas J; Hemminger, John C

    2011-08-04

    Molecular-level insight into the dissociation of nitric acid in water is obtained from X-ray photoelectron spectroscopy and first-principles molecular dynamics (MD) simulations. Our combined studies reveal surprisingly abrupt changes in solvation configurations of undissociated nitric acid at approximately 4 M concentration. Experimentally, this is inferred from shifts of the N1s binding energy of HNO(3)(aq) as a function of concentration and is associated with variations in the local electronic structure of the nitrogen atom. It also shows up as a discontinuity in the degree of dissociation as a function of concentration, determined here from the N1s photoelectron signal intensity, which can be separately quantified for undissociated HNO(3)(aq) and dissociated NO(3)(-)(aq). Intermolecular interactions within the nitric acid solution are discussed on the basis of MD simulations, which reveal that molecular HNO(3) interacts remarkably weakly with solvating water molecules at low concentration; around 4 M there is a turnover to a more structured solvation shell, accompanied by an increase in hydrogen bonding between HNO(3) and water. We suggest that the driving force behind the more structured solvent configuration of HNO(3) is the overlap of nitric acid solvent shells that sets in around 4 M concentration.

  7. TES/Aura L3 Nitric Acid (HNO3) Daily V3 (TL3HNOD)

    Atmospheric Science Data Center

    2015-10-30

    ... Access: OPeNDAP Parameters:  HNO3 Volume Mixing Ratio Precision Vertical Resolution Order Data:  ... Google Earth Visualizations Giovanni Visualization - Level3 Daily Related Data:  Level 3 ...

  8. TES/Aura L3 Nitric Acid (HNO3) Daily V4 (TL3HNOD)

    Atmospheric Science Data Center

    2015-10-30

    ... Access: OPeNDAP Parameters:  HNO3 Volume Mixing Ratio Precision Vertical Resolution Order Data:  ... Google Earth Visualizations Giovanni Visualization - Level3 Daily Related Data:  Level 3 ...

  9. Vapor pressures of solid hydrates of nitric acid - Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Worsnop, Douglas R.; Fox, Lewis E.; Zahniser, Mark S.; Wofsy, Steven C.

    1993-01-01

    Thermodynamic data are presented for hydrates of nitric acid: HNO3.H2O, HNO3.2H2O, HNO3.3H2O, and a higher hydrate. Laboratory data indicate that nucleation and persistence of metastable HNO3.2H2O may be favored in polar stratospheric clouds over the slightly more stable HNO3.3H2O. Atmospheric observations indicate that some polar stratospheric clouds may be composed of HNO3.2H2O and HNO3.3H2O. Vapor transfer from HNO3.2H2O to HNO3.3H2O could be a key step in the sedimentation of HNO3, which plays an important role in the depletion of polar ozone.

  10. Composition and freezing of aqueous H2SO4/HNO3 solutions under polar stratospheric conditions

    NASA Technical Reports Server (NTRS)

    Beyer, K. D.; Seago, S. W.; Chang, H. Y.; Molina, M. J.

    1994-01-01

    The results of laboratory investigations of the freezing behavior of aqueous acid solutions indicate that in the stratosphere H2SO/H2O aerosol droplets would not freeze at temperatures above the ice frost point in the absence of HNO3; however, in the presence of typical levels of HNO3 liquid sulfuric acid aerosols take up significant amounts of HNO3 and H2O vapors and freeze much more readily. This is a consequence of the very rapid change in composition of the liquid droplets as the temperature drops to within two to three degrees of the equilibrium temperature at which HNO3 and H2O vapors would co-condense to form a liquid solution. In the high latitude stratosphere this HNO3/H2O 'dew point' is typically around 192-194 K at 100 mbar.

  11. Chemical Corrosion of Liquid-Phase Sintered SiC in Acidic/Alkaline Solutions Part 1. Corrosion in HNO3 Solution

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Zhang, Ming; He, Xinnong; Tang, Wenming

    2016-03-01

    The corrosion behavior of the liquid-phase sintered SiC (LPS-SiC) was studied by dipping in 3.53 mol/L HNO3 aqueous solution at room temperature and 70 °C, respectively. The weight loss, strength reduction and morphology evolution of the SiC specimens during corroding were revealed and also the chemical corrosion process and mechanism of the SiC specimens in the acidic solution were clarified. The results show that the corrosion of the LPS-SiC specimens in the HNO3 solution is selective. The SiC particles are almost free from corrosion, but the secondary phases of BaAl2Si2O8 (BAS) and Y2Si2O7 are corroded via an acid-alkali neutralization reaction. BAS has a higher corrosion rate than Y2Si2O7, resulting in the formation of the bamboo-leaf-like corrosion pits. As the SiC specimens etched in the HNO3 solution at room temperature for 75 days, about 80 μm thickness corrosion layer forms. The weight loss and bending strength reduction of the etched SiC specimens are 2.6 mg/cm2 and 52%, respectively. The corrosion of the SiC specimens is accelerated in the 70 °C HNO3 solution with a rate about five times bigger than that in the same corrosion medium at room temperature.

  12. The ν_3 and ν_4 Bands of Nitric Acid (HNO_3) at 7.6 μm for Atmospheric Studies

    NASA Astrophysics Data System (ADS)

    Perrin, A.; Flaud, J. M.; Ridolfi, M.; Carlotti, M.

    2012-06-01

    Nitric acid (HNO_3) plays an important role as a reservoir molecule of the NO_x (nitrogen oxides) species in the stratosphere. The three strongest infrared bands of nitric acid are located at 11 μm (ν_5 and 2ν_9 bands), 7.6 μm (the ν_3 and ν_4 bands at 1326 and 1303 cm-1) and 5.8 μm (ν_2 band). Although two times weaker than those located at 7.6 and 5.8 μm, the 11 μm region is the only one which is used for nitric acid retrievals in the atmosphere by several satellite instruments like MIPAS (Michelson Interferometer for Passive Atmospheric Sounding on ENVISAT) or ACE-FTS (ACE Fourier transform spectrometer on SCISAT). This is because the available spectroscopic parameters for HNO_3 in the HITRAN and GEISA databases are of very good quality in this spectral region. Of the two remaining bands, the 7.6 μm one is only partly masked by water, and therefore can be used also for nitric acid retrievals in the upper stratosphere. Moreover, because of their large difference in band intensity, combining measurements at 11 μm and 7.6 μm could maximize informations on the vertical distribution of HNO_3 in the atmosphere. However at 7.6 μm the spectroscopic parameters available in the HITRAN and GEISA databases are are not so good. Indeed, these parameters originate from a list generated more than 20 years ago. The low quality of the list at 7.6 μm prevents HNO_3 retrievals and severely affects the retrievals of several species absorbing in the 7.5-7.7 μm region, like SO_2. This work is a new and more accurate investigation of the line positions and intensities for the ν_3 and ν_4 bands of nitric acid located at 1326.187 and 1303.074 cm-1). For this task, we used new infrared laboratory data combined with a new theoretical model. Examples showing substantial improvements will be given. [1] Rothman et al. J. Quant. Spectrosc. Radiat. Transf., 110, 533-572, 2009 [2] Jacquinet et al. J. Quant. Spectrosc. Radiat. Transf., 112, 2395-2445, 2011 [3] A. Perrin, O. Lado

  13. Novel polysiloxane resin functionalized with dicyclohexano-18-crown-6 (DCH18C6): Synthesis, characterization and extraction of Sr(II) in high acidity HNO3 medium.

    PubMed

    Ye, Gang; Bai, Feifei; Wei, Jichao; Wang, Jianchen; Chen, Jing

    2012-07-30

    A novel kind of polysiloxane resin functionalized with dicyclohexano-18-crown-6 (DCH18C6) was synthesized through a post-modification approach. The DCH18C6 moieties bearing amino groups were firstly prepared, followed by covalent grafting to a silica precursor P-(CH(2))(3)-Cl (Where P represents a 3-dimentional polymerized silica matrix) based on nucleophilic substitution reaction. (29)Si and (13)C solid-state NMR, FT-IR, XPS, TGA, ESEM and elemental analysis were employed to systematically characterize the structure, thermal property and surface morphology of the functionalized resin. The results indicated that the DCH18C6 ligands were successfully bonded to the polysiloxane resin with a satisfactory grafting degree (33.6wt.%). Due to the robust organosilica framework and the covalent immobilization of the ligands, the functionalized resin had excellent thermal stability and acid resistance. Batch experiments showed that the resin could effectively separate Sr(II) in high acidity mediums. The distribution coefficient (K(d)) of 43.6cm(3)/g could be achieved in 5.0mol/L HNO(3) solution. The influences of contact time and acidity of HNO(3) on the resin's extraction performance were examined. The reusability and the selectivity to Sr(II) over interference ions were investigated. The DCH18C6-functionalized resin might be potentially applied for the radiostrontium removal in the high level liquid waste (HLLW).

  14. Fast-response airborne in situ measurements of HNO3 during the Texas 2000 Air Quality Study

    NASA Astrophysics Data System (ADS)

    Neuman, J. A.; Huey, L. G.; Dissly, R. W.; Fehsenfeld, F. C.; Flocke, F.; Holecek, J. C.; Holloway, J. S.; Hübler, G.; Jakoubek, R.; Nicks, D. K.; Parrish, D. D.; Ryerson, T. B.; Sueper, D. T.; Weinheimer, A. J.

    2002-10-01

    Nitric acid (HNO3) was measured from an aircraft in the planetary boundary layer and free troposphere up to 7 km on 14 flights during the Texas Air Quality Study in August and September 2000. HNO3 mixing ratios were measured at 1 Hz using a fast-response chemical ionization mass spectrometer with SiF5- reagent ions. HNO3 measurement using this highly selective ion chemistry is insensitive to water vapor and is not degraded by interferences from other species. Rapid time response (1 s) was achieved using a heated Teflon inlet. In-flight standard addition calibrations from a HNO3 permeation source were used to determine the instrument sensitivity of 1.1 ± 0.1 ion counts pptv-1 s-1 over the duration of the study. Contributions to the HNO3 signal from instrument artifacts were accounted for by regularly performing in-flight instrument background checks, where HNO3 was removed from the ambient air sample by diverting the sampled air though a nylon wool scrubber. Measurement inaccuracy, which is determined from uncertainties in the standard addition calibrations, was ±10%. Measurement precision at low HNO3 levels was ±25 pptv (1σ) for the 1 Hz data and ±9 pptv for 10 s averages of the 1 s measurements. Coincident in situ measurements of other reactive nitrogen species are used to examine NOy partitioning and HNO3 formation during this month long measurement campaign. The sum of the individually measured reactive nitrogen species is shown to be in agreement with the measured NOy. HNO3 formation in plumes from electric utility power plants, urban areas, and petrochemical facilities was studied. The observed differences in the fractional contribution of HNO3 to NOy in plumes from different anthropogenic source types are discussed.

  15. Mass accommodation coefficient measurements for HNO3, HCl and N2O5 on water, ice and aqueous sulfuric acid droplet surfaces

    NASA Technical Reports Server (NTRS)

    Worsnop, Douglas; Zahniser, Mark; Kolb, Charles; Watson, Lyn; Vandoren, Jane; Jayne, John; Davidovits, Paul

    1988-01-01

    Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.

  16. Spectroscopic study of HNO3 dissociation on ice.

    PubMed

    Marchand, Patrick; Marcotte, Guillaume; Ayotte, Patrick

    2012-12-13

    A detailed spectroscopic study of HNO(3):H(2)O binary amorphous mixtures, and of the adsorption of HNO(3) onto ice, is reported. Using a classical optics model, the extent of intermixing and of ionic dissociation of adsorbed HNO(3), which forms a strong acid with liquid water, is determined as a function of HNO(3) coverage and temperature. Even at temperatures as low as 45 K, where intermixing is limited to at most a few molecular layers at the interface, ionic dissociation of adsorbed HNO(3) is observed to be extensive. While some amount of molecularly adsorbed HNO(3) is observed at the surface of ice at 45 K, its ionic dissociation occurs irreversibly upon heating the ice substrate to 120 K. The molecularly adsorbed state of HNO(3) is not restored upon cooling, suggesting HNO(3) is a metastable entity at the surface of ice. Therefore, despite ionic dissociation of HNO(3) being thermodynamically favored, it appears to be kinetically inhibited at the surface of amorphous solid water at temperatures below 120 K.

  17. Uptake of HNO3 on hexane and aviation kerosene soots.

    PubMed

    Talukdar, Ranajit K; Loukhovitskaya, Ekaterina E; Popovicheva, Olga B; Ravishankara, A R

    2006-08-10

    The uptake of HNO(3) on aviation kerosene (TC-1) soot was measured as a function of temperature (253-295 K) and the partial pressure of HNO(3), and the uptake of HNO(3) on hexane soot was studied at 295 K and over a limited partial pressure of HNO(3). The HNO(3) uptake was mostly reversible and did not release measurable amounts of gas-phase products such as HONO, NO(3), NO(2) or N(2)O(5). The heat of adsorption of HNO(3) on soot was dependent on the surface coverage. The isosteric heats of adsorption, Delta(0)H(isosteric), were determined as a function of coverage. Delta(0)H(isosteric) values were in the range -16 to -13 kcal mol(-1). The heats of adsorption decrease with increasing coverage. The adsorption data were fit to Freundlich and to Langmuir-Freundlich isotherms. The heterogeneity parameter values were close to 0.5, which suggested that a HNO(3) molecule can occupy two sites on the surface with or without being dissociated and that the soot surface could be nonuniform. Surface FTIR studies on the interaction of soot with HNO(3) did not reveal formation of any minor product such as organic nitrate or nitro compound on the soot surface. Using our measured coverage, we calculate that the partitioning of gas-phase nitric acid to black carbon aerosol is not a significant loss process of HNO(3) in the atmosphere.

  18. Uptake of HNO3 on aviation kerosene and aircraft engine soot: influences of H2O or/and H2SO4.

    PubMed

    Loukhovitskaya, Ekaterina E; Talukdar, Ranajit K; Ravishankara, A R

    2013-06-13

    The uptake of HNO3 on aviation kerosene soot (TC-1 soot) was studied in the absence and presence of water vapor at 295 and 243 K. The influence of H2SO4 coating of the TC-1 soot surface on HNO3 uptake was also investigated. Only reversible uptake of HNO3 was observed. HONO and NO2, potential products of reactive uptake of HNO3, were not observed under any conditions studied here. The uptake of nitric acid increased slightly with relative humidity (RH). Coating of the TC-1 soot surface with sulfuric acid decreased the uptake of HNO3 and did not lead to displacement of H2SO4 from the soot surface. A limited set of measurements was carried out on soot generated by aircraft engine combustor (E-soot) with results similar to those on TC-1 soot. The influence of water on HNO3 uptake on E-soot appeared to be more pronounced than on TC-1 soot. Our results suggest that HNO3 loss in the upper troposphere due to soot is not significant except perhaps in aircraft exhaust plumes. Our results also suggest that HNO3 is not converted to either NO2 or HONO upon its uptake on soot in the atmosphere.

  19. Heterogeneous kinetics of H2O, HNO3 and HCl on HNO3 hydrates (α-NAT, β-NAT, NAD) in the range 175-200 K

    NASA Astrophysics Data System (ADS)

    Iannarelli, Riccardo; Rossi, Michel J.

    2016-09-01

    Experiments on the title compounds have been performed using a multidiagnostic stirred-flow reactor (SFR) in which the gas phase as well as the condensed phase has been simultaneously investigated under stratospheric temperatures in the range 175-200 K. Wall interactions of the title compounds have been taken into account using Langmuir adsorption isotherms in order to close the mass balance between deposited and desorbed (recovered) compounds. Thin solid films at 1 µm typical thickness have been used as a proxy for atmospheric ice particles and have been deposited on a Si window of the cryostat, with the optical element being the only cold point in the deposition chamber. Fourier transform infrared (FTIR) absorption spectroscopy in transmission as well as partial and total pressure measurement using residual gas mass spectrometry (MS) and sensitive pressure gauges have been employed in order to monitor growth and evaporation processes as a function of temperature using both pulsed and continuous gas admission and monitoring under SFR conditions. Thin solid H2O ice films were used as the starting point throughout, with the initial spontaneous formation of α-NAT (nitric acid trihydrate) followed by the gradual transformation of α- to β-NAT at T > 185 K. Nitric acid dihydrate (NAD) was spontaneously formed at somewhat larger partial pressures of HNO3 deposited on pure H2O ice. In contrast to published reports, the formation of α-NAT proceeded without prior formation of an amorphous HNO3 / H2O layer and always resulted in β-NAT. For α- and β-NAT, the temperature-dependent accommodation coefficient α(H2O) and α(HNO3), the evaporation flux Jev(H2O) and Jev(HNO3) and the resulting saturation vapor pressure Peq(H2O) and Peq(HNO3) were measured and compared to binary phase diagrams of HNO3 / H2O in order to afford a thermochemical check of the kinetic parameters. The resulting kinetic and thermodynamic parameters of activation energies for evaporation (Eev) and

  20. Vapour pressures of H2SO4/HNO3/HCI/HBr/H2O solutions to low stratospheric temperatures

    SciTech Connect

    Luo, B.; Carslaw, K.S.; Peter, T.; Clegg, S.L. |

    1995-02-01

    Vapor pressures of H2O, HNO3, HCl and HBr over supercooled aqueous mixtures with sulfuric acid have been calculated using an activity coefficient model, for 185 K less than T less than 235 K, 0 less than wt% (H2SO4) + wt% (HNO3) less than 70, and assuming HCl and HBr to be minor constituents. Predicted vapor pressures agree well with most laboratory data, and give confidence in the validity of the model. The results are parameterized as simple formulae, which reproduce the model results to within 40% and cover the entire stratospherically relevant range of composition and temperature.

  1. Laboratory studies of infrared absorption by NO2 and HNO3

    NASA Technical Reports Server (NTRS)

    Murcray, D. G.; Goldman, A.; Bonomo, F.

    1975-01-01

    Data concerning the quantitative absorption in the 11 and 22 micron region by HNO3 were obtained. Results are presented indicating the temperature dependence of these bands of HNO3 vapor. The 21.8 micron absorption bands of HNO3 vapor at 40 C are discussed along with the integrated intensity and line parameters for the 6.2 micron band of NO2.

  2. Nucleation and growth of HNO3-3H2O particles in the polar stratosphere

    NASA Technical Reports Server (NTRS)

    Wofsy, Steven C.; Gobbi, Gian Paolo; Salawitch, Ross J.; Mcelroy, Michael B.

    1990-01-01

    Growth of nitric acid trihydrate (NAT) particles on background stratospheric aerosols is examined for an isolated air parcel cooled at a uniform rate. During the process of nucleation, the saturation ratio of HNO3 vapor reaches a maximum value between 2 and 15, corresponding to supercooling by 1-4 K. If cooling rates exceed 0.5-1 K/day, small particles of NAT are produced. A major fraction of the available condensation nuclei is activated and removal of HNO3 by gravitational settling is slow. If cooling rates are less than 0.5-1 K/day, the number of aerosols that nucleate is reduced, leading to differential growth of large NAT particles. Observations of 5 micron radius particles in clouds at temperatures above the water frost point may reflect condensation of NAT on ice particles that fall through a column of air as it is cooled. Rapid condensation of HNO3 on ice particles is promoted by the high supersaturation attained during nucleation and maintained during subsequent cooling. This process provides a mechanism for irreversible removal of HNO3.

  3. Efficiency enhancement of graphene/silicon-pillar-array solar cells by HNO3 and PEDOT-PSS.

    PubMed

    Feng, Tingting; Xie, Dan; Lin, Yuxuan; Zhao, Haiming; Chen, Yu; Tian, He; Ren, Tianling; Li, Xiao; Li, Zhen; Wang, Kunlin; Wu, Dehai; Zhu, Hongwei

    2012-03-21

    A single-layer graphene film was grown on copper foil by chemical vapor deposition and transferred onto a silicon-pillar-array (SPA) substrate to make a Schottky junction solar cell. The SPA substrate was specifically designed to suppress reflectance and enhance light absorption. The energy conversion efficiency of the prepared graphene/SPA solar cells achieved a maximum of 2.90% with a junction area of 0.09 cm(2). HNO(3) was employed to dope the graphene in the solar cells, and the time dependence of HNO(3) treatment on the cell performance was studied. Poly(3,4-ethylenedioxythiophene) polystyrenesulfonic acid (PEDOT-PSS) was also introduced in graphene/SPA solar cells by spin coating on top of the graphene film, and its modification on the cell performance was characterized. The results show that both HNO(3) and the PEDOT-PSS film could enhance the energy conversion efficiency of graphene/SPA solar cells.

  4. Laboratory studies of HNO3/H2O mixtures at low temperatures

    NASA Technical Reports Server (NTRS)

    Hanson, David; Mauersberger, Konrad

    1988-01-01

    The possibility of stratospheric HN3 condensing out of the gas-phase at low temperatures has become important in the chemical explanations of the rapid loss of Antarctic ozone in spring. Consequently, knowledge about the behavior of the vapor pressures of water and HNO3 over HNO3/water mixtures at stratospheric temperatures is needed to determine if HNO3 could condense, and by how much the HNO3 vapor pressure could be depressed. Laboratory investigations of vapor pressures above HNO3/water mixtures are described. Vapor pressures were initially measured over liquid and frozen bulk mixtures contained in a glass still which was attached to a stainless steel vacuum chamber. The total pressure in the chamber was monitored with a precision pressure sensor, and the vapor pressures of HNO3, water and impurities were analyzed with a mass spectrometer beam system. In a second set of experiments, vapor deposits were made to produce ice and the mono- and trihydrate of HNO3. Further data and conclusions are presented.

  5. Freezing temperatures of H2SO4/HNO3/H2O mixtures: Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Song, Naihui

    1994-01-01

    The freezing temperatures of H2SO4/HNO3/H2O mixtures were systematically documented. Nitric acid was found to affect freezing significantly. Measurements show that nitric acid can cause substantial supercooling over a broad composition range. However, some ternary compositions, like to those in polar stratospheric clouds (PSCs), have high freezing temperatures. The freezing of PSC particles could be controlled by the temperature and vapor pressure of both nitric acid and water in a non-linear way. Formation of polar stratospheric clouds may be forecasted on the basic of conditions of temperature and vapor contents of water and nitric acid.

  6. Enhanced performance of PEDOT:PSS/n-Si hybrid solar cell by HNO3 treatment

    NASA Astrophysics Data System (ADS)

    Zhao, Haiming; Xie, Dan; Feng, Tingting; Zhao, Yuanfan; Xu, Jianlong; Li, Xinming; Zhu, Hongwei; Ren, Tianling

    2014-03-01

    In this study, a poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/n-Si hybrid solar cell is fabricated via spin coating and treatment with HNO3 vapor. It is found that after the HNO3 treatment, the hybrid solar cell shows much better performance with an open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (FF), and power conversion efficiency (η) of 555.34 mV, 23.61 mA/cm2, 0.54, and 8.81%, respectively. The conversion efficiency is nearly two times larger than that before HNO3 treatment. The possible reason is that HNO3 could significantly reduce the resistivity of the spin-coated PEDOT:PSS. The effect of HNO3 treatment time on the PEDOT:PSS/n-Si HSC’s performance is also investigated.

  7. The reduction of HNO3 by volatile organic compounds emitted by motor vehicles

    NASA Astrophysics Data System (ADS)

    Rutter, A. P.; Malloy, Q. G. J.; Leong, Y. J.; Gutierrez, C. V.; Calzada, M.; Scheuer, E.; Dibb, J. E.; Griffin, R. J.

    2014-04-01

    Nitric acid (HNO3) was reduced in a flow tube by volatile organic carbon compounds (VOCs) generated from engine oil vapor. The primary reaction product was believed to be HONO. The reaction was not enhanced when Teflon® Raschig rings were added to the flow tube to increase surface area, thereby showing the reaction to be homogeneous under the conditions studied. The HONO formation observed ranged between 0.1 and 0.6 ppb h-1, with a mean of 0.3 ± 0.1 ppb h-1, for typical HNO3 concentrations of 4-5 ppb and estimated concentrations of the reactive components in the engine oil vapor between 200 and 300 ppt. The observations in this study compare well to a recently published field study conducted in Houston that observed average formation rates of 0.6 ± 0.3 ppb h-1. Water vapor was found to decrease the HONO formation rate by ˜0.1 ppb h-1 for every 1% increase in the water mixing ratio.

  8. Measuring tropospheric HNO3 - Problems and prospects for Nylon filter and mist chamber techniques

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Vijgen, A. S.; Harriss, R. C.

    1990-01-01

    A series of laboratory and field measurements was performed to evaluate the mist chamber technique for determining tropospheric HNO3 concentrations. Both the mist chamber and standard Nylon filter techniques exhibit high collection efficiency and excellent agreement measuring HNO3 vapors from a permeation source. When simultaneously sampling ambient air in eastern Virginia, the Nylon filter measured an average of 70 percent higher HNO3 concentration than the mist chamber technique. The results indicate that O3 causes a low-level positive artifact interference in HNO3 measurements performed with the filter technique. This O3-induced error is small, however, compared to the large difference between atmospheric HNO3 concentrations determined with the two techniques. It is hypothesized that unidentified (organic?) nitrogen species in the atmosphere react for form NO3(-) on the filter and this phenomenon may interfere with Nylon filter measurements of HNO3 vapor. These potential interferences did not appear to affect measurements of HNO3 with the mist chamber method.

  9. 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.

  10. Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

    1993-01-01

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

  11. Miniaturizing and automation of free acidity measurements for uranium (VI)-HNO3 solutions: Development of a new sequential injection analysis for a sustainable radio-analytical chemistry.

    PubMed

    Néri-Quiroz, José; Canto, Fabrice; Guillerme, Laurent; Couston, Laurent; Magnaldo, Alastair; Dugas, Vincent

    2016-10-01

    A miniaturized and automated approach for the determination of free acidity in solutions containing uranium (VI) is presented. The measurement technique is based on the concept of sequential injection analysis with on-line spectroscopic detection. The proposed methodology relies on the complexation and alkalimetric titration of nitric acid using a pH 5.6 sodium oxalate solution. The titration process is followed by UV/VIS detection at 650nm thanks to addition of Congo red as universal pH indicator. Mixing sequence as well as method validity was investigated by numerical simulation. This new analytical design allows fast (2.3min), reliable and accurate free acidity determination of low volume samples (10µL) containing uranium/[H(+)] moles ratio of 1:3 with relative standard deviation of <7.0% (n=11). The linearity range of the free nitric acid measurement is excellent up to 2.77molL(-1) with a correlation coefficient (R(2)) of 0.995. The method is specific, presence of actinide ions up to 0.54molL(-1) does not interfere on the determination of free nitric acid. In addition to automation, the developed sequential injection analysis method greatly improves the standard off-line oxalate complexation and alkalimetric titration method by reducing thousand fold the required sample volume, forty times the nuclear waste per analysis as well as the analysis time by eight fold. These analytical parameters are important especially in nuclear-related applications to improve laboratory safety, personnel exposure to radioactive samples and to drastically reduce environmental impacts or analytical radioactive waste.

  12. The Reduction of HNO3 to HONO by Volatile Organic Compounds Associated with Rush Hour Traffic

    NASA Astrophysics Data System (ADS)

    Rutter, A. P.; Malloy, Q.; Scheuer, E.; Gutierrez, C.; Calzada, M.; Dibb, J. E.; Griffin, R. J.

    2012-12-01

    Nitrous acid (HONO) is an important source of OH radicals in urban environments. However, the sources of HONO are not completely understood, which makes modeling urban atmospheric chemistry difficult. During a previous field study in Houston, TX a correlation was observed between increases in HONO and organic aerosol freshly emitted by motor vehicle traffic during morning rush hours (Ziemba et al., 2010). This source of HONO could not be explained by primary HONO emissions, and the hypothesis was drawn that the HONO was being formed from the reduction of HNO3 by the organic aerosols emitted by motor vehicles. To test this hypothesis, nitric acid (HNO3) was combined in a flow tube with aerosols made from automobile engine oil, which were used as a model for the organic aerosols emitted by rush hour traffic. Reduction of the HNO3 to HONO was observed, although the reaction was found to occur with the volatile organic carbon compounds (VOCs) found in the aerosol vapor, and not the particle surfaces. To explore this further Teflon raschig rings were added to the flow tube to increase surface area but the reaction was not enhanced, confirming the reaction to be homogeneous. The HONO formation observed ranged between 0.1 and 0.5 ppb hr-1 with a mean of 0.3±0.1 ppb hr-1, for typical nitric acid concentrations of 4-5 ppb and estimated concentrations of the reactive components in the engine oil vapor of between 200 and 300 ppt. The observations in this study compared well to the cited field study which observed formation rates between 0.05 and 0.5 ppb hr-1 with an average of 0.3±0.15 ppb hr-1. Water vapor was found to decrease the HONO formation rate by 0.1 ppb hr-1 for every1% of increase in the water mixing ratio. Reference Ziemba L.D., Dibb J.E., Griffin R.J., Anderson C.H., Whitlow S.I., Lefer B.L., Rappenglueck B., and Flynn J. (2010) Heterogeneous conversion of nitric acid to nitrous acid on the surface of primary organic aerosol in an urban atmosphere. Atmospheric

  13. Antarctic ozone - Meteoric control of HNO3

    NASA Technical Reports Server (NTRS)

    Prather, Michael J.; Rodriguez, Jose M.

    1988-01-01

    Atmospheric circulation leads to an accumulation of debris from meteors in the Antarctic stratosphere at the beginning of austral spring. The major component of meteoric material is alkaline, comprised predominantly of the oxides of magnesium and iron. These metals may neutralize the natural acidity of stratospheric aerosols, remove nitric acid from the gas phase, and bond it as metal nitrates in the aerosol phase. Removal of nitric acid vapor has been previously shown to be a critical link in the photochemical depletion of ozone in the Antarctic spring, by allowing for increased catalytic loss from chlorine and bromine.

  14. A Study on the Passivation Behavior and Semiconducting Properties of Gamma Titanium Aluminide in 0.1 N H2SO4, HNO3, and HClO4 Acidic Solutions

    NASA Astrophysics Data System (ADS)

    Memarbashi, S.; Saebnoori, E.; Shahrabi, T.

    2014-03-01

    The study focuses on the passivation behavior of single-gamma-phase titanium aluminide in acidic solutions with a particular emphasis on the role of oxidizing strength in characteristics of passive layer. The report includes potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies along with Mott-Schottky analysis in order to determine the corrosion behavior of the alloy and the semiconducting properties of the scale formed during exposure to acidic environment. Passive current density measured from potentiodynamic polarization curve, polarization resistance ( R p) estimated by EIS, defect density, and flatband potential drawn from Mott-Schottky analysis are mainly used in estimating the ability of passive film formed on alloy in protecting it against high corrosion rates in Sulfuric acid (a non-oxidizing acid), perchloric acid, and nitric acid (oxidizing acid with different oxidizing strength). The results show that passive current density ( i pass) in Sulfuric acid is 2.67 × 10-5 A cm-2, which is 2.5 and 3 times greater than the values obtained in perchloric acid ( i pass = 9.91 × 10-6) and nitric acid ( i pass = 7.98 × 10-6), respectively. EIS data reveal that the value of R p in sulfuric acid (20 kΩ cm2) is about three and five times smaller than that its value in perchloric acid and Nitric acid, respectively. Mott-Schottky analysis shows that the passive layer exhibits an n-type semiconducting characteristics irrespective of acidic environment. The greatest and the smallest values of donor density ( N D) are obtained for the passive scale formed in sulfuric acid ( N D, H2SO4 = 18.36 × 1019) and nitric acid ( N D, HNO3 = 13.13 × 1019), respectively. The report concludes that characteristics of the passive scale are directly affected by reduction potential of the acid, which is the criterion of its oxidizing strength. An increase in the oxidizing strength of the acidic solution results in formation of more protective and less

  15. Impact of future land cover changes on HNO3 and O3 surface dry deposition

    NASA Astrophysics Data System (ADS)

    Verbeke, T.; Lathière, J.; Szopa, S.; de Noblet-Ducoudré, N.

    2015-07-01

    Dry deposition is a key component of surface-atmosphere exchange of compounds, acting as a sink for several chemical species. Meteorological factors, chemical properties of the trace gas considered and land surface properties are strong drivers of dry deposition efficiency and variability. Under both climatic and anthropogenic pressure, the vegetation distribution over the Earth has been changing a lot over the past centuries, and could be significantly altered in the future. In this study, we perform a modeling investigation of the potential impact of land-cover changes between present-day (2006) and the future (2050) on dry deposition rates, with special interest for ozone (O3) and nitric acid vapor (HNO3), two compounds which are characterized by very different physico-chemical properties. The 3-D chemistry transport model LMDz-INCA is used, considering changes in vegetation distribution based on the three future projections RCPs 2.6, 4.5 and 8.5. The 2050 RCP 8.5 vegetation distribution leads to a rise up to 7 % (+0.02 cm s-1) in VdO3 and a decrease of -0.06 cm s-1 in VdHNO3 relative to the present day values in tropical Africa, and up to +18 and -15 % respectively in Australia. When taking into account the RCP 4.5 scenario, which shows dramatic land cover change in Eurasia, VdHNO3 increases by up to 20 % (annual-mean value) and reduces VdO3 by the same magnitude in this region. When analyzing the impact of dry deposition change on atmospheric chemical composition, our model calculates that the effect is lower than 1 ppb on annual mean surface ozone concentration, for both for the RCP8.5 and RCP2.6 scenarios. The impact on HNO3 surface concentrations is more disparate between the two scenarios, regarding the spatial repartition of effects. In the case of the RCP 4.5 scenario, a significant increase of the surface O3 concentration reaching locally up to 5 ppb (+5 %) is calculated on average during the June-August period. This scenario induces also an increase of

  16. Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

    NASA Technical Reports Server (NTRS)

    Santee, M. L.; Read, W. G.; Waters, J. W.; Froidevaux, L.; Manney, G. L.; Flower, D. A.; Jarnot, R. F.; Harwood, R. S.; Peckham, G. E.

    1995-01-01

    Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone 'hole' is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

  17. Rate of reaction of OH with HNO3

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Ravishankara, A. R.; Kreutter, N. M.; Shah, R. C.; Nicovich, J. M.; Thompson, R. L.; Wuebbles, D. J.

    1981-01-01

    Measurements of the kinetics of the reaction of OH with HNO3, and mechanisms of HNO3 removal from the stratosphere, are reported. Bimolecular rate constants were determined at temperatures between 224 and 366 K by monitoring the concentrations of OH radicals produced by HNO3 photolysis and HNO3 according to their resonance fluorescence and 184.9-nm absorption, respectively. The rate constant measured at 298 K is found to be somewhat faster than previously accepted values, with a negative temperature dependence. Calculations of a one-dimensional transport-kinetic atmospheric model on the basis of the new rate constant indicate reductions in O3 depletion due to chlorofluoromethane release and NOx injection, of magnitudes dependent on the nature of the reaction products.

  18. Persistent Water-Nitric Acid Condensate with Saturation Water Vapor Pressure Greater than That of Hexagonal Ice.

    PubMed

    Gao, Ru-Shan; Gierczak, Tomasz; Thornberry, Troy D; Rollins, Andrew W; Burkholder, James B; Telg, Hagen; Voigt, Christiane; Peter, Thomas; Fahey, David W

    2016-03-10

    A laboratory chilled mirror hygrometer (CMH), exposed to an airstream containing water vapor (H2O) and nitric acid (HNO3), has been used to demonstrate the existence of a persistent water-nitric acid condensate that has a saturation H2O vapor pressure greater than that of hexagonal ice (Ih). The condensate was routinely formed on the mirror by removing HNO3 from the airstream following the formation of an initial condensate on the mirror that resembled nitric acid trihydrate (NAT). Typical conditions for the formation of the persistent condensate were a H2O mixing ratio greater than 18 ppm, pressure of 128 hPa, and mirror temperature between 202 and 216 K. In steady-state operation, a CMH maintains a condensate of constant optical diffusivity on a mirror through control of only the mirror temperature. Maintaining the persistent condensate on the mirror required that the mirror temperature be below the H2O saturation temperature with respect to Ih by as much as 3 K, corresponding to up to 63% H2O supersaturation with respect to Ih. The condensate was observed to persist in steady state for up to 16 h. Compositional analysis of the condensate confirmed the co-condensation of H2O and HNO3 and thereby strongly supports the conclusion that the Ih supersaturation is due to residual HNO3 in the condensate. Although the exact structure or stoichiometry of the condensate could not be determined, other known stable phases of HNO3 and H2O are excluded as possible condensates. This persistent condensate, if it also forms in the upper tropical troposphere, might explain some of the high Ih supersaturations in cirrus and contrails that have been reported in the tropical tropopause region.

  19. The vapor pressures of supercooled NHO3/H2O solutions. [in polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Hanson, David R.

    1990-01-01

    A procedure utilizing the Gibbs-Duhem relation is used to extrapolate vapor pressures of supercooled HNO3 mixtures to 190 K. Values of A and B from the equation logP = A - B/T are presented for solutions between 0.20 and 0.25 mole fraction HNO3. In the stratosphere, if sufficient HNO3 vapor is present because it has not come into equilibrium with the nitric acid trihydrate, supercooled nitric acid solutions could condense at temperatures up to 1.5 + or - 0.8 K above the ice point.

  20. First characterization and validation of FORLI-HNO3 vertical profiles retrieved from IASI/Metop

    NASA Astrophysics Data System (ADS)

    Ronsmans, Gaétane; Langerock, Bavo; Wespes, Catherine; Hannigan, James W.; Hase, Frank; Kerzenmacher, Tobias; Mahieu, Emmanuel; Schneider, Matthias; Smale, Dan; Hurtmans, Daniel; De Mazière, Martine; Clerbaux, Cathy; Coheur, Pierre-François

    2016-09-01

    Knowing the spatial and seasonal distributions of nitric acid (HNO3) around the globe is of great interest and allows us to comprehend the processes regulating stratospheric ozone, especially in the polar regions. Due to its unprecedented spatial and temporal sampling, the nadir-viewing Infrared Atmospheric Sounding Interferometer (IASI) is capable of sounding the atmosphere twice a day globally, with good spectral resolution and low noise. With the Fast Optimal Retrievals on Layers for IASI (FORLI) algorithm, we are retrieving, in near real time, columns as well as vertical profiles of several atmospheric species, among which is HNO3. We present in this paper the first characterization of the FORLI-HNO3 profile products, in terms of vertical sensitivity and error budgets. We show that the sensitivity of IASI to HNO3 is highest in the lower stratosphere (10-20 km), where the largest amounts of HNO3 are found, but that the vertical sensitivity of IASI only allows one level of information on the profile (degrees of freedom for signal, DOFS; ˜ 1). The sensitivity near the surface is negligible in most cases, and for this reason, a partial column (5-35 km) is used for the analyses. Both vertical profiles and partial columns are compared to FTIR ground-based measurements from the Network for the Detection of Atmospheric Composition Change (NDACC) to characterize the accuracy and precision of the FORLI-HNO3 product. The profile validation is conducted through the smoothing of the raw FTIR profiles by the IASI averaging kernels and gives good results, with a slight overestimation of IASI measurements in the upper troposphere/lower stratosphere (UTLS) at the six chosen stations (Thule, Kiruna, Jungfraujoch, Izaña, Lauder and Arrival Heights). The validation of the partial columns (5-35 km) is also conclusive with a mean correlation of 0.93 between IASI and the FTIR measurements. An initial survey of the HNO3 spatial and seasonal variabilities obtained from IASI

  1. HNO3 profiles obtained during the EASOE campaign

    NASA Technical Reports Server (NTRS)

    Murcray, F. J.; Starkey, J. R.; Williams, W. J.; Matthews, W. A.; Schmidt, U.; Aimedieu, P.; Camy-Peyret, C.

    1994-01-01

    A small cryogenically cooled spectrometer system designed to obtain atmospheric emission spectra in the 7.5 micrometer to 13.0 micrometer region was flown piggyback on 9 balloon flights from ESRANGE (67.9 deg N, 21.2 deg E) during the European Arctic Stratospheric Ozone Experiment (EASOE) campaign. Initial analysis of the spectra obtained has been concentrated on obtaining HNO3 profiles for the various flights. HNO3 profiles for 17 December 1991, 9 January 1992, 22 January 1992, 5 February 1992 and 14 March 1992 are presented.

  2. Comparison of the CIBA HNO_3 model with UARS observations

    NASA Astrophysics Data System (ADS)

    Gille, J.; Bailey, P.; Massie, S.; Roche, A.; Kumer, J.; Lyjak, L.

    The CIRA HNO_3 model is based on the 7 months of data from the LIMS experiment on Nimbus 7. Now CLAES and ISAMS, two instruments on UARS, are providing further observations. Preliminary CLAES results are here compared with the CIRA model. There is agreement on the broad features of the HNO_3 distribution. CLAES data provide the first direct observations of the Northern Hemisphere summer, and of the atmosphere poleward of 64 S. Because the data are still being evaluated and improved, it is premature to draw any quantitative conclusions at this time.

  3. Uptake of HNO3 to deliquescent sea-salt particles

    NASA Astrophysics Data System (ADS)

    Guimbaud, C.; Arens, F.; Gutzwiller, L.; Gäggeler, H. W.; Ammann, M.

    2002-06-01

    The uptake of HNO3 to deliquescent airborne sea-salt particles (RH = 55%, P = 760 torr, T = 300 K) at concentrations from 2 to 575 ppbv is measured in an aerosol flow tube using 13N as a tracer. Small particles (~ 70 nm diameter) are used in order to minimize the effect of diffusion in the gas phase on the mass transfer. Below 100 ppbv, an uptake coefficient (gupt) of 0.50 ± 0.20 is derived. At higher concentrations, the uptake coefficient decreases along with the consumption of aerosol chloride. Data interpretation is further supported by using the North American Aerosol Inorganics Model (AIM), which predicts the aqueous phase activities of ions and the gas-phase partial pressures of H2O, HNO3, and HCl at equilibrium for the NaCl/HNO3/H2O system. These simulations show that the low concentration data are obtained far from equilibrium, which implies that the uptake coefficient derived is equal to the mass accommodation coefficient under these conditions. The observed uptake coefficient can serve as input to modeling studies of atmospheric sea-salt aerosol chemistry. The main sea-salt aerosol burden in the marine atmosphere is represented by coarse mode particles (> 1 mm diameter). This implies that diffusion in the gas-phase is the limiting step to HNO3 uptake until the sea-salt has been completely processed.

  4. Heterogeneous conversion of N2O5 to HNO3 in the post-Mount Pinatubo eruption stratosphere

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Gunson, M. R.; Abrams, M. C.; Lowes, L. L.; Zander, R.; Mahieu, E.; Goldman, A.; Ko, M. K. W.; Rodriguez, J. M.; Sze, N. D.

    1994-01-01

    Simultaneous stratospheric volume mixing ration (VMR) profiles of dinitrogen pentoxide (N2O5) and nitric acid (HNO3) at sunrise between 25 deg N and 15 deg S latitude and profiles of HNO3 at sunset between 42 deg S and 53 deg S latitude have been derived from 0.01/cm resolution infrared solar occultation spectra recorded 9.5 months after the massive eruption of the Mount Pinatubo volcano in the Philippine Islands. The measurements were obtained by the atmospheric trace molecule spectroscopy (ATMOS) Fourier transform spectrometer during the ATLAS 1 shuttle mission (March 24 to April 2, 1992). The measured HNO3 VMRs are higher at all altitudes and latitudes than corresponding values measured by the limb infrared monitor of the stratosphere (LIMS) instrument during the same season in 1979, when the aerosol loading was near background levels. The largest relative increase in the HNO3 VMR occurred near the equator at 30-km altitude, where the ATMOS/ATLAS 1 values are about a factor of 2 higher than the LIMS measurements. Two-dimensional model calculations show that the increase in HNO3 and the ATMOS/ATLAS 1 measurement of a steep decrease in the N2O5 VMR below 30 km can be explained by the enhanced conversion of N2O5 to HNO3 on the surfaces of the Mount Pinatubo sulfate aerosols. Our profile results demonstrate the global impact of the N2O5 + H2O yields 2HNO3 heterogeneous reaction in altering the partitioning of stratospheric odd nitrogen after a major volcanic eruption.

  5. Heterogeneous conversion of N2O5 to HNO3 in the post-Mount Pinatubo eruption stratosphere

    NASA Astrophysics Data System (ADS)

    Rinsland, C. P.; Gunson, M. R.; Abrams, M. C.; Lowes, L. L.; Zander, R.; Mahieu, E.; Goldman, A.; Ko, M. K. W.; Rodriguez, J. M.; Sze, N. D.

    1994-04-01

    Simultaneous stratospheric volume mixing ratio (VMR) profiles of dinitrogen pentoxide (N2O5) and nitric acid (HNO3) at sunrise between 25°N and 15°S latitude and profiles of HNO3 at sunset between 42°S and 53°S latitude have been derived from 0.01 cm-1 resolution infrared solar occultation spectra ? months after the massive eruption of the Mount Pinatubo volcano in the Philippine Islands. The measurements were obtained by the atmospheric trace molecule spectroscopy (ATMOS) Fourier transform spectrometer during the ATLAS 1 shuttle mission (March 24 to April 2, 1992). The measured HNO3 VMRs are higher at all altitudes and latitudes than corresponding values measured by the limb infrared monitor of the stratosphere (LIMS) instrument during the same season in 1979, when the aerosol loading was near background levels. The largest relative increase in the HNO3 VMR occurred near the equator at 30-km altitude, where the ATMOS/ATLAS 1 values are about a factor of 2 higher than the LIMS measurements. Two-dimensional model calculations show that the increase in HNO3 and the ATMOS/ATLAS 1 measurement of a steep decrease in the N2O5 VMR below 30 km can be explained by the enhanced conversion of N2O5 to HNO3 on the surfaces of the Mount Pinatubo sulfate aerosols. Our profile results demonstrate the global impact of the N2O5 + H2O → 2HNO3 heterogeneous reaction in altering the partitioning of stratospheric odd nitrogen after a major volcanic eruption.

  6. Competitive Adsorption of HNO3 and HCl On/in Water Clusters and Ice

    NASA Astrophysics Data System (ADS)

    Balci, M.; Uras-Aytemiz, N.

    2009-04-01

    Solvation and ionization of strong acids such as HX (X=Cl, Br), HNO3 etc. have been subjected to many researchers (see for example refs. 1, 2, and references therein). In this study, the competitive adsorption of two strong acids, namely, HCl and HNO3 on/in the water clusters and the surface of crystalline ice slab containing 72 water molecules were investigated at the average temperatures below 140 K. The main tool of this study is on-the-fly molecular dynamics as implemented in the density functional code QUICKSTEP (3) which is part of CP2K package (4). The small water clusters containing both HNO3 and HCl with up to five water molecules were further checked with MP2 level ab initio calculations. The results will be discussed in terms of dynamics, structures, energetics and spectroscopic perspectives. 1. Buch, V.; Sadlej, J.; Aytemiz-Uras, N.; Devlin, J. P., The Journal of Physical Chemistry A 2002, 106, 9374. 2. Escribano, R.; Couceiro, M.; Gómez, P. C.; Carrasco, E.; Moreno, M. A.; Herrero, V. J., The Journal of Physical Chemistry A 2003, 107, 651. 3. CP2K, http://cp2k.berlios.de (2000-2004). 4. VandeVondele, J.; Krack, M.; Mohamed, F.; Parrinello, M.; Chassaing, T.; Hutter, J., Comp. Phys. Comm. 2005, 167, 103. This work was supported by TUBITAK (Project number: 107T044)

  7. Transport of atmospheric NOx and HNO3 over Cape Town

    NASA Astrophysics Data System (ADS)

    Abiodun, B. J.; Ojumu, A. M.; Jenner, S.; Ojumu, T. V.

    2013-05-01

    Cape Town, the most popular tourist city in Africa, usually experiences air pollution with unpleasant odour in winter. Previous studies have associated the pollution with local emission of pollutants within the city. The present study examines the transport of atmospheric pollutants (NOx and HNO3) over South Africa and shows how the transport of pollutants from the Mpumalanga Highveld may contribute to the pollution in Cape Town. The study analysed observation data (2001-2008) from Cape Town air quality network and simulation data (2001-2004) from regional climate model (RegCM4) over southern Africa. The simulation accounts for the influence of complex topography, atmospheric condition, and atmospheric chemistry on emission and transport of pollutants over southern Africa. Flux budget analysis was used to examine whether Cape Town is a source or sink for NOx and HNO3 during the extreme pollution events. The results show that extreme pollution events over Cape Town are associated with the low-level (surface-850 hPa) transport of NOx from the Mpumalanga Highveld to Cape Town, and with a tongue of high concentration of HNO3 that extends from the Mpumalanga Highveld to Cape Town along the south coast of South Africa. The prevailing atmospheric conditions during the extreme pollution events feature an upper-level (700 hPa) anticyclonic flow over South Africa and a low-level col over Cape Town. The anticyclonic flow induces a strong subsidence motion, which prevents vertical mixing of the pollutants and caps high concentration of pollutants close to the surface as they are transported from the Mpumalanga Highveld toward Cape Town, while the col accumulates the pollutants over the city. This study shows that Cape Town can be a sink for the NOx and HNO3 during extreme pollution events and suggests that the accumulation of pollutants transported from other areas (e.g. Mpumalanga Highveld) may contribute substantially to the air pollution in Cape Town.

  8. Ground-based infrared measurements of HNO3 total column abundances - Long-term trend and variability

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Zander, R.; Demoulin, P.

    1991-01-01

    The long-term trend and variability of the total column amount of atmospheric nitric acid (HNO3) have been investigated. The study was based on time series of infrared solar absorption spectra recorded at two sites, the International Scientific Station of the Jungfraujoch (ISSJ) in the Swiss Alps (altitude 3.6 km, latitude 46.5 N, longitude 8.0 E) and the National Solar Observatory McMath solar telescope facility on Kitt Peak (altitude 2.1 km, latitude 31.9 N, longitude 111.6 W), Arizona. Measurements of HNO3 absorption features recorded at Kitt Peak between 1980 and 1990 and measurements of the same features in ISSJ solar spectra obtained in June 1951 and June 1986 to June 1990 provide quantitative estimates of the long-term trend in the HNO3 total vertical column. It is found that the trend deduced for each site is equal to zero within the measurement uncertainty. The modern ISSJ measurements show that the fitted trend is (-0.16 + or - 0.50) percent/yr, 2 sigma, which indicates that there has been no detectable change in HNO3 total column over three decades. The Kitt Peak measurements show marked variability in the HNO3 total column, but no obvious seasonal cycle is observed.

  9. Model/Data Comparisons of NO2 and HNO3

    NASA Astrophysics Data System (ADS)

    Remsberg, E. E.; Natarajan, M.; Thompson, R. E.; Gordley, L. L.

    2001-05-01

    NASA Reference Publication 1292 [Prather and Remsberg, 1993] contains reports of the stratospheric model simulations of NOy for 1980, when the effects of volcanic aerosols on the partitioning of NOy should have been minimal. Those model runs included heterogeneous chemistry on background aerosols. Model values of NO2 and HNO3 were compared with those from the archived Nimbus 7 LIMS dataset, and the models exhibited the seasonal asymmetry that was observed for the LIMS HNO3. Still there were model/data differences that did not seem to be related solely to the variations among the model transport fields. Since then, we have updated the LIMS emissivity tables (spectroscopic parameters) and developed new algorithms for retrieving the profiles of the LIMS species, and we will show that there is improved agreement between these new data and the early results from most of the models. However, because there have also been improvements since 1992 in model transport of N2O and in the relevant chemical mechanisms for the generation and partitioning of NOy, it is recommended that the various models be rerun for the 1980 case and recompared with this latest version of the LIMS dataset.

  10. Participation of HNO3 CIMS Instrument in the Sage III Ozone Loss and Validation Experiment (SOLVE)

    NASA Technical Reports Server (NTRS)

    Eisele, F. L.

    2001-01-01

    This project was part of a larger SOLVE project led by Paul Wennberg at California Institute of Technology. The work completed on this project included participating in the installation and preflight testing of a new chemical ionization mass spectrometer for measuring gas and particle phase nitric acid on the ER-2. The investigators subsequently participated in SOLVE where additional instrument improvements were made and a substantial data set was generated. The two Georgia Tech investigators that participated in this work (Fred Eisele and Dave Tanner) had previously been responsible for much of the design and construction of the ion source and mass spectrometer which would be used to measure HNO3 in SOLVE, with Caltech focusing on inlets, calibration, gas supplies/pumping computer control, and overall integration. Thus, a similar focus remained during the SOLVE measurements though all investigators worked on most if not all aspects of the instrument at some point in the mission. Some of the more interesting results from the study included measurements of nitric acid on what are thought to be 5-20 microns diameter individual particles which could supply a local mechanism for HNO3 removal, Nitric acid measurements on SOLVE were completed as a collaborative effort with a great deal of overlap between this project and the larger parent project led by Paul Wennberg. As such, the instrumentation used, its operation, and the resulting measurements are far more fully discussed in the attached report (appendix A) which describes the joint SOLVE nitric acid measurement effort.

  11. Impact of future land-cover changes on HNO3 and O3 surface dry deposition

    NASA Astrophysics Data System (ADS)

    Verbeke, T.; Lathière, J.; Szopa, S.; de Noblet-Ducoudré, N.

    2015-12-01

    Dry deposition is a key component of surface-atmosphere exchange of compounds, acting as a sink for several chemical species. Meteorological factors, chemical properties of the trace gas considered and land surface properties are strong drivers of dry deposition efficiency and variability. Under both climatic and anthropogenic pressure, the vegetation distribution over the Earth has been changing a lot over the past centuries and could be significantly altered in the future. In this study, we perform a modeling investigation of the potential impact of land-cover changes between the present day (2006) and the future (2050) on dry deposition velocities at the surface, with special interest for ozone (O3) and nitric acid (HNO3), two compounds which are characterized by very different physicochemical properties. The 3-D chemistry-transport model LMDz-INCA is used, considering changes in vegetation distribution based on the three future projections, RCPs 2.6, 4.5 and 8.5, and present-day (2007) meteorology. The 2050 RCP 8.5 vegetation distribution leads to a rise of up to 7 % (+0.02 cm s-1) in the surface deposition velocity calculated for ozone (Vd,O3) and a decrease of -0.06 cm s-1 in the surface deposition velocity calculated for nitric acid (Vd,HNO3) relative to the present-day values in tropical Africa and up to +18 and -15 %, respectively, in Australia. When taking into account the RCP 4.5 scenario, which shows dramatic land-cover change in Eurasia, Vd,HNO3 increases by up to 20 % (annual-mean value) and reduces Vd,O3 by the same magnitude in this region. When analyzing the impact of surface dry deposition change on atmospheric chemical composition, our model calculates that the effect is lower than 1 ppb on annual-mean surface ozone concentration for both the RCP 8.5 and RCP 2.6 scenarios. The impact on HNO3 surface concentrations is more disparate between the two scenarios regarding the spatial repartition of effects. In the case of the RCP 4.5 scenario, a

  12. Kinetics of heterogeneous reaction of CaCO3 particles with gaseous HNO3 over a wide range of humidity.

    PubMed

    Liu, Y; Gibson, E R; Cain, J P; Wang, H; Grassian, V H; Laskin, A

    2008-02-21

    Heterogeneous reaction kinetics of gaseous nitric acid (HNO3) with calcium carbonate (CaCO3) particles was investigated using a particle-on-substrate stagnation flow reactor (PS-SFR). This technique utilizes the exposure of substrate deposited, isolated, and narrowly dispersed particles to a gas mixture of HNO3/H2O/N2, followed by microanalysis of individual reacted particles using computer-controlled scanning electron microscopy with energy-dispersive X-ray analysis (CCSEM/EDX). The first series of experiments were conducted at atmospheric pressure, room temperature and constant relative humidity (40%) with a median dry particle diameter of Dp = 0.85 mum, particle loading densities 2 x 104 HNO3 concentrations of 7, 14, and 25 ppb. The apparent, pseudo first-order rate constant for the reaction was determined from oxygen enrichment in individual particles as a function of particle loading. Quantitative treatment of the data using a diffusion-kinetic model yields a lower limit to the net reaction probability gammanet >/= 0.06 (x3//2). In a second series of experiments, HNO3 uptake on CaCO3 particles of the same size was examined over a wide range of relative humidity, from 10 to 80%. The net reaction probability was found to increase with increasing relative humidity, from gammanet >/= 0.003 at RH = 10% to 0.21 at 80%.

  13. Measurements of HCl and HNO3 with the new research aircraft HALO - Quantification of the stratospheric contribution to the O3 and HNO3 budget in the UT/LS

    NASA Astrophysics Data System (ADS)

    Jurkat, Tina; Kaufmann, Stefan; Voigt, Christiane; Zahn, Andreas; Schlager, Hans; Engel, Andreas; Bönisch, Harald; Dörnbrack, Andreas

    2013-04-01

    Dynamic and chemical processes modify the ozone (O3) budget of the upper troposphere/lower stratosphere, leading to locally variable O3 trends. In this region, O3 acts as a strong greenhouse gas with a net positive radiative forcing. It has been suggested, that the correlation of the stratospheric tracer hydrochloric acid (HCl) with O3 can be used to quantify stratospheric O3 in the UT/LS region (Marcy et al., 2004). The question is, whether the stratospheric contribution to the nitric acid (HNO3) budget in the UT/LS can be determined by a similar approach in order to differentiate between tropospheric and stratospheric sources of HNO3. To this end, we performed in situ measurements of HCl and HNO3 with a newly developed Atmospheric chemical Ionization Mass Spectrometer (AIMS) during the TACTS (Transport and Composition in the UTLS) / ESMVal (Earth System Model Validation) mission in August/September 2012. The linear quadrupole mass spectrometer deployed aboard the new German research aircraft HALO was equipped with a new discharge source generating SF5- reagent ions and an in-flight calibration allowing for accurate, spatially highly resolved trace gas measurements. In addition, sulfur dioxide (SO2), nitrous acid (HONO) and chlorine nitrate (ClONO2) have been simultaneously detected with the AIMS instrument. Here, we show trace gas distributions of HCl and HNO3 measured during a North-South transect from Northern Europe to Antarctica (68° N to 65° S) at 8 to 15 km altitude and discuss their latitude dependence. In particular, we investigate the stratospheric ozone contribution to the ozone budget in the mid-latitude UT/LS using correlations of HCl with O3. Differences in these correlations in the subtropical and Polar regions are discussed. A similar approach is used to quantify the HNO3 budget of the UT/LS. We identify unpolluted atmospheric background distributions and various tropospheric HNO3 sources in specific regions. Our observations can be compared to

  14. The detection of large HNO3-containing particles in the winter Arctic stratosphere.

    PubMed

    Fahey, D W; Gao, R S; Carslaw, K S; Kettleborough, J; Popp, P J; Northway, M J; Holecek, J C; Ciciora, S C; McLaughlin, R J; Thompson, T L; Winkler, R H; Baumgardner, D G; Gandrud, B; Wennberg, P O; Dhaniyala, S; McKinney, K; Peter, T; Salawitch, R J; Bui, T P; Elkins, J W; Webster, C R; Atlas, E L; Jost, H; Wilson, J C; Herman, R L; Kleinböhl, A; von König, M

    2001-02-09

    Large particles containing nitric acid (HNO3) were observed in the 1999/2000 Arctic winter stratosphere. These in situ observations were made over a large altitude range (16 to 21 kilometers) and horizontal extent (1800 kilometers) on several airborne sampling flights during a period of several weeks. With diameters of 10 to 20 micrometers, these sedimenting particles have significant potential to denitrify the lower stratosphere. A microphysical model of nitric acid trihydrate particles is able to simulate the growth and sedimentation of these large sizes in the lower stratosphere, but the nucleation process is not yet known. Accurate modeling of the formation of these large particles is essential for understanding Arctic denitrification and predicting future Arctic ozone abundances.

  15. Measurement of OH, H2SO4, MSA, and HNO3 Aboard the P-3B Aircraft

    NASA Technical Reports Server (NTRS)

    Eisele, F. L.

    2003-01-01

    This paper addresses the measurement of OH, H2SO4, MSA, and HNO3 aboard the P-3B aircraft under the following headings: 1) Performance Report; 2) Highlights of OH, H2SO4, and MSA Measurements Made Aboard the NASA P-3B During TRACE-P; 3) Development and characteristics of an airborne-based instrument used to measure nitric acid during the NASA TRACE-P field experiment.

  16. Heterogeneous reactions of NO2 and HNO3 on oxides and mineral dust: A combined laboratory and modeling study

    NASA Astrophysics Data System (ADS)

    Underwood, G. M.; Song, C. H.; Phadnis, M.; Carmichael, G. R.; Grassian, V. H.

    2001-08-01

    This study combines laboratory measurements and modeling analysis to quantify the role of heterogeneous reactions of gaseous nitrogen dioxide and nitric acid on mineral oxide and mineral dust particles in tropospheric ozone formation. At least two types of heterogeneous reactions occur on the surface of these particles. Upon initial exposure of the oxide to NO2 there is a loss of NO2 from the gas phase by adsorption on the particle surface, i.e., NO2(g) → NO2(a). As the reaction proceeds, a reduction of gaseous NO2 to NO, NO2 (g) → NO (g) is found to occur. Initial uptake coefficients γ0 for NO2 on the surface of these particles have been measured at 298 K using a Knudsen cell reactor coupled to a mass spectrometer. For the oxides studied, α,γ-Al2O3, α,γ-Fe2O3, TiO2, SiO2, CaO, and MgO, γ0 ranges from <4×10-10 for SiO2 to 2×10-5 for CaO with most values in the 10-6 range. For authentic samples of China loess and Saharan sand, similar reactivity to the oxides is observed with γ0 values of 2×10-6 and 1×10-6, respectively. For HNO3 the reactivity is 1-2 orders of magnitude higher. Using these laboratory measurements, the impact of heterogeneous reactions of NO2 and HNO3 on mineral dust in tropospheric ozone formation and on O3-precursor relationships is assessed using a time-dependent, multiphase chemistry box model. Simulations with and without heterogeneous reactions were conducted to evaluate the possible influence of these heterogeneous reactions on ambient levels. Results show that values of the initial uptake for NO2 and HNO3, adjusted for roughness effects, must be greater than 10-4 to have an appreciable impact on NOx, HNO3, and O3 concentrations for the conditions modeled here. Thus the measured uptake coefficients for NO2 on dry surfaces are just below the lower limit to have an impact on the photochemical oxidant cycle, while the heterogeneous reactivity of HNO3 is sufficiently large to have an effect. Under conditions of high mineral dust

  17. Unveiling the shape-diversified silicon nanowires made by HF/HNO3 isotropic etching with the assistance of silver.

    PubMed

    Chen, Chia-Yun; Wong, Ching-Ping

    2015-01-21

    Hydrofluoric (HF)/nitric (HNO3)/acetic (CH3COOH) acid, normally referred to as the HNA method, is a widely utilized technique for performing isotropic etching on silicon (Si) in industrial Si-based processing and device construction. Here, we reported a novel etching strategy based on a HF/HNO3 process with the assistance of silver (Ag) nano-seeds, offering good controllability in preparing diversified Si nanostructure arrays with particularly smooth top surfaces. The involved mechanism was visualized by systematically investigating both the time and temperature dependencies on the etching kinetics with various ratios of HF to HNO3. Moreover, by testing different Ag(+)-ion containing oxidants on Si etching, we have re-examined the state-of-the-art metal-assisted chemical etching (MaCE) using HF/AgNO3 etchants. In contrast with previous reports, we found that the interplay of hole injections from Ag(+) and NO3(-) ions to the valence band of Si collectively contributes to the unidirectional dissolution of Si. Finally, we explored the engineering of the Ag nano-seeds to regularize the orientation of the etched nanowires formed on non-Si (100) wafers, which further provides a reliable pathway for constructing the desired morphologies of one-dimensional Si nanostructures regardless of wafer orientation.

  18. FTIR Spectroscopy of HNO3 and NO2 Relevant to Stratospheric Wake Analysis

    NASA Technical Reports Server (NTRS)

    Abina, Rafiu A.; Misra, Prabhakar; Okabe, Hideo; Chu, P. M.; Sams, Robert L.

    1997-01-01

    The Fourier Transform Infrared (FTIR) technique has been employed to measure absolute concentrations of nitric acid (HNO3) and nitrogen dioxide (NO2) with 1/cm resolution and an absorption pathlength of 4 m under quasi-static and flow conditions at atmospheric pressure and room temperature. Water features seen under quasi-static conditions diminished in intensity under flowing conditions. Nitric acid was observed in the 1660-1760/cm range, while nitrogen dioxide was detected both in the 1536-1660 and 1213-1400/cm ranges. Concentrations of nitrogen dioxide and nitric acid were determined to be 11.9 and 4.35 parts per million (ppm), respectively, with an uncertainty of 0.2 ppm. Experiments are underway with a 10 m cell to measure the absorption of nitric acid, water, sulfur dioxide, hydrochloric acid and ammonia on various materials such as glass, teflon, stainless steel and aluminum used for implementation of the flow system. Such materials will be used for the measurements of stratospheric trace gases by the Quartz Crystal Microbalance (QCM) and Surface Acoustic Wave (SAW) devices.

  19. Temperature dependent absorption cross-sections of HNO3 and N2O5

    NASA Technical Reports Server (NTRS)

    Rattigan, Oliver V.; Harwood, Matthew H.; Jones, Rod L.; Cox, Richard A.

    1994-01-01

    Absorption cross-sections for HNO3 and N2O5 have been measured in the wavelength region 220-450 nm, using a dual beam diode array spectrometer with a spectral resolution of 0.3 nm. The results for both compounds are in good agreement with recommended values at room temperature. However, the cross-sections of both HNO3 and N2O5 show a marked reduction with decreasing temperature in the range 295-233 K. The calculated photolysis rate of HNO3 at the low temperatures and high solar zenith angles characteristic of the polar winter and spring is significantly lower than previously estimated.

  20. Vapor-deposited water and nitric acid ices

    NASA Astrophysics Data System (ADS)

    Leu, Ming-Taun; Keyser, Leon F.

    Ices formed by vapor deposition have been the subject of numerous laboratory investigations in connection with snow and glaciers on the ground, ice clouds in the terrestrial atmosphere, surfaces of other planets and their satellites, and the interstellar medium. In this review we will focus on these specific subjects: (1) heterogeneous chemistry on the surfaces of polar stratospheric clouds (PSCs) and (2) surfaces of satellites of the outer planets in our solar system. Stratospheric ozone provides a protective shield for mankind and the global biosphere from harmful ultraviolet solar radiation. In past decades, theoretical atmospheric models for the calculation of ozone balance frequently used only homogeneous gas-phase reactions in their studies. Since the discovery of the Antarctic ozone hole in 1985, however, it has been demonstrated that knowledge of heterogeneous reactions on the surface of PSCs is definitely needed to understand this significant natural event due to the anthropogenic emission of chlorofluorocarbons (CFCs). We will briefly discuss the experimental techniques for the investigation of heterogeneous chemistry on ice surfaces carried out in our laboratories. The experimental apparatus used include: several flow-tube reactors, an electron-impact ionization mass spectrometer, a Fourier transform infrared spectrometer, a BET adsorption apparatus, and a scanning environmental electron microscope. The adsorption experiments and electron microscopic work have demonstrated that the vapor-deposited ices are highly porous. Therefore, it is necessary to develop theoretical models for the elucidation of the uptake and reactivity of trace gases in porous ice substrates. Several measurements of uptake and reaction probabilities of these trace gases on water ices and nitric acid ices have been performed under ambient conditions in the upper troposphere and lower stratosphere, mainly in the temperature range 180-220 K. The trace gases of atmospheric importance

  1. Detection of stratospheric HNO3 and NO2 response to short-term solar ultraviolet variability

    NASA Astrophysics Data System (ADS)

    Keating, G. M.; Nicholson, J., III; Brasseur, G.; de Rudder, A.; Schmailzl, U.

    1986-07-01

    It is pointed out that variations in the solar ultraviolet irradiance with a period equal to or approximately one-half of the rotation period of the sun are currently observed by satellite monitoring. Information regarding the response of stratospheric species to solar ultraviolet variability is indispensable for an understanding of the photochemical behavior of the middle atmosphere. Relations are considered between LIMS (limb infrared monitor of the stratosphere) measurements of HNO3 and NO2, and the SBUV (solar backscatter ultraviolet) measurements of short-term variations in 205-nm radiation. It is found that the response of HNO3 is much stronger than, but in the opposite sense to the ozone response, while the NO2 response is in the opposite sense to the HNO3 response. Model calculations predict large variations in HNO3 over the 11-yr solar cycle.

  2. Measurements of HNO3 and N2O5 using ion drift-chemical ionization mass spectrometry during the MILAGRO/MCMA-2006 campaign

    NASA Astrophysics Data System (ADS)

    Zheng, J.; Zhang, R.; Fortner, E. C.; Volkamer, R. M.; Molina, L.; Aiken, A. C.; Jimenez, J. L.; Gaeggeler, K.; Dommen, J.; Dusanter, S.; Stevens, P. S.; Tie, X.

    2008-11-01

    An ion drift-chemical ionization mass spectrometer (ID-CIMS) was deployed in Mexico City between 7 and 31 March to measure gas-phase nitric acid (HNO3) and dinitrogen pentoxide (N2O5 during the Mexico City Metropolitan Area (MCMA)-2006 field campaign. The observation site was located at the Instituto Mexicano del Petróleo in the northern part of Mexico City urban area with major emissions of pollutants from residential, vehicular and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and early morning. The concentration of HNO3 increased steadily from around 09:00 a.m. central standard time (CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early afternoon, and then declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS) showed a good agreement between the two HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with submicron-sized aerosol nitrate, suggesting that the gas-particle partitioning process was a major factor in determining the gaseous HNO3 concentration. Losses by irreversible reactions with mineral dust and via dry deposition also could be important at this site. Most of the times during the MCMA 2006 field campaign, N2O5 was found to be below the detection limit (about 30 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio at the surface (>100 ppb) during the night. An exception occurred on 26 March 2006, when about 40 ppt N2O5 was observed during the late afternoon and early evening hours under cloudy conditions before the build-up of NO at the surface site. The results revealed that during the MCMA-2006 field campaign HNO3 was primarily produced from the reaction of OH with NO2 and regulated by gas/particle transfer and dry deposition. The production of HNO3 from N2O5 hydrolysis during the nighttime was small because of

  3. Theoretical study of atmospheric clusters: HNO3:HCl:H2O

    NASA Astrophysics Data System (ADS)

    Gomez, P. C.; Escribano, R. M.; Galvez, O.

    2009-04-01

    Water, nitric acid and hydrogen chloride play an important role in several atmospheric processes, as individual species, and also interacting in the complex reactions related to ozone depletion in polar stratospheric clouds (PSC). The atmospheric importance of the ternary system HCl:HNO3:H2O was recognized long ago [1]. It is also known that HCl attaches to the surface of PSC particles formed by nitric acid hydrates in what can be considered the first step of the heterogeneous reactions leading to the release of the active chlorine molecule [2]. Recently, HCl was detected dissolved in liquid particles with HNO3/H2O by in situ measurements in the Artic stratosphere [3]. The study of simple models including these three species at a high level of theory can be the first step towards the understanding of all possible kinds of bonding and structures that can arise among these molecules, and can constitute the embryo of more complex mixtures with higher amounts of water or variable proportions of their constituents. This kind of calculations have been successfully performed in the past [4,5]. We present in this contribution our results on the structure and spectroscopical properties of the many different ways that these molecules can be bonded in what are predicted to be thermodynamically stable species. The calculations are performed by density functional methods (B3LYP) using Dunning's quadruple-zeta augmented correlated consisted basis sets (aug-cc-pVQZ). This work has been supported by the Spanish Ministry of Education, Projects FIS2007-61686 and CTQ2008-02578/BQU. We wish to thank also CESGA (Centro de Supercomputacion de Galicia), where some of these calculations were carried out. References: [1] O. B. Toon, P. Hamill, R. P. Turco, J. Pinto. Geophys. Res. Lett. 1986, 13, 1284. [2] Molina, M. J.; Zhang, R.; Wooldridge, P. J.; McMahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D. Science 1993, 261,1418. [3] C. Weiser, K. Mauersberger, J. Schreiner, N. Larsen, F

  4. Unveiling the shape-diversified silicon nanowires made by HF/HNO3 isotropic etching with the assistance of silver

    NASA Astrophysics Data System (ADS)

    Chen, Chia-Yun; Wong, Ching-Ping

    2014-12-01

    Hydrofluoric (HF)/nitric (HNO3)/acetic (CH3COOH) acid, normally referred to as the HNA method, is a widely utilized technique for performing isotropic etching on silicon (Si) in industrial Si-based processing and device construction. Here, we reported a novel etching strategy based on a HF/HNO3 process with the assistance of silver (Ag) nano-seeds, offering good controllability in preparing diversified Si nanostructure arrays with particularly smooth top surfaces. The involved mechanism was visualized by systematically investigating both the time and temperature dependencies on the etching kinetics with various ratios of HF to HNO3. Moreover, by testing different Ag+-ion containing oxidants on Si etching, we have re-examined the state-of-the-art metal-assisted chemical etching (MaCE) using HF/AgNO3 etchants. In contrast with previous reports, we found that the interplay of hole injections from Ag+ and NO3- ions to the valence band of Si collectively contributes to the unidirectional dissolution of Si. Finally, we explored the engineering of the Ag nano-seeds to regularize the orientation of the etched nanowires formed on non-Si (100) wafers, which further provides a reliable pathway for constructing the desired morphologies of one-dimensional Si nanostructures regardless of wafer orientation.Hydrofluoric (HF)/nitric (HNO3)/acetic (CH3COOH) acid, normally referred to as the HNA method, is a widely utilized technique for performing isotropic etching on silicon (Si) in industrial Si-based processing and device construction. Here, we reported a novel etching strategy based on a HF/HNO3 process with the assistance of silver (Ag) nano-seeds, offering good controllability in preparing diversified Si nanostructure arrays with particularly smooth top surfaces. The involved mechanism was visualized by systematically investigating both the time and temperature dependencies on the etching kinetics with various ratios of HF to HNO3. Moreover, by testing different Ag

  5. MIPAS database: new HNO3 line parameters at 7.6  µm validated with MIPAS satellite measurements

    NASA Astrophysics Data System (ADS)

    Perrin, Agnès; Flaud, Jean-Marie; Ridolfi, Marco; Vander Auwera, Jean; Carlotti, Massimo

    2016-05-01

    Improved line positions and intensities have been generated for the 7.6 µm spectral region of nitric acid. They were obtained relying on a recent reinvestigation of the nitric acid band system at 7.6 µm and comparisons of HNO3 volume mixing ratio profiles retrieved from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) limb emission radiances in the 11 and 7.6 µm domains. This has led to an improved database called MIPAS-2015. Comparisons with available laboratory information (individual line intensities, integrated absorption cross sections, and absorption cross sections) show that MIPAS-2015 provides an improved description of the 7.6 µm region of nitric acid. This study should help to improve HNO3 satellite retrievals by allowing measurements to be performed simultaneously in the 11 and 7.6 µm micro-windows. In particular, it should be useful to analyze existing MIPAS and IASI spectra as well as spectra to be recorded by the forthcoming Infrared Atmospheric Sounding Interferometer - New Generation (IASI-NG) instrument.

  6. Investigation of Interfacial and Bulk Dissociation of HBr, HCl, and HNO3 Using Density Functional Theory-Based Molecular Dynamics Simulations

    SciTech Connect

    Baer, Marcel; Tobias, Douglas J.; Mundy, Christopher J.

    2014-12-18

    In this study we investigate the free energy barrier associated with the dissociation of strong acids, XH (HBr, HCl and HNO3) deprotonation, and subsequent formation of ionpairs, X–___H3O+ in the vicinity of the air-water interface. We will show that the free energy for acid dissociation for HCl and HNO3 show significant differences at the air-water than under bulk solvation conditions producing a picture where at the interface associated molecular species can be stable. For the strongest acid we consider, HBr the more traditional picture of acids is preserved in the vicinity of the air-water interface. Our results have implications for our understanding of acids, and their surface tensions at the air-water interface.

  7. Quantum chemical study of ternary mixtures of: HNO3:H2SO4:H2O

    NASA Astrophysics Data System (ADS)

    Verdes, M. A.; Gómez, P. C.; Gálvez, O.

    2009-04-01

    Water, nitric acid and sulfuric acid are important atmospheric species as individual species and as hydrogen-bonded aggregates involved in many physical-chemical processes both superficial and bulk. The importance of heterogeneous chemical reactions taking place on ice surfaces, either solid water or solid water plus nitric or sulfuric acid, is well established now in relation to the ozone-depleting mechanisms. Also the importance of liquid droplets formed by HNO3.H2SO4.H2O as components of PSC was soon recognized [1-3]. Finally the physical properties of finely divided aqueous systems is an interesting and active field of research in which theoretical information on the microphysical domain systems may help to understand and rationalize the wealth of experimental information. This can also be the initial step in the study of more complex mixtures with higher amounts of water or variable proportions of their constituents. This kind of calculations have been successfully performed in the past[4]. We present here our results on the structure and spectroscopic and thermodynamic properties of the energy-lowest lying structures among those thermodynamically stable formed by linking the acids plus water. The calculations have been carried out by means of DFT methods (in particular the successful B3LYP) using different basis sets that contain appropriate sets of polarization and diffuse functions up to quadruple-Z quality (Dunninǵs aug-cc-pVQZ). Careful assessment of the dependability of the methodology used has been carried out. This work has been supported by the Spanish Ministry of Education, Projects FIS2007-61686 and CTQ2008-02578/BQU References: [1] Carslaw, K. S. et al.: Geophys. Res. Lett. 21, 2479-2482, 1994 [2] Drdla, K. Et al. :Geophys. Res. Lett. 21, 2473-2478, 1994 [3] Tabazadeh, A. et al.: Geophys. Res. Lett 21, 1619-1622, 1994 [4] Escribano, R et al.: J. J. Chem. Phys A 2003, 107, 652.

  8. Experimental and theoretical studies of the interaction of gas phase nitric acid and water with a self-assembled monolayer.

    PubMed

    Moussa, S G; Stern, A C; Raff, J D; Dilbeck, C W; Tobias, D J; Finlayson-Pitts, B J

    2013-01-14

    Nitric acid in air is formed by atmospheric reactions of oxides of nitrogen and is removed primarily through deposition to surfaces, either as the gas or after conversion to particulate nitrate. Many of the surfaces and particles have organic coatings, but relatively little is known about the interaction of nitric acid with organic films. We report here studies of the interaction of gaseous HNO(3) with a self-assembled monolayer (SAM) formed by reacting 7-octenyltrichlorosilane [H(2)C=CH(CH(2))(6)SiCl(3)] with the surface of a germanium infrared-transmitting attenuated total reflectance (ATR) crystal that was coated with a thin layer of silicon oxide (SiO(x)). The SAM was exposed at 298 ± 2 K to dry HNO(3) in a flow of N(2), followed by HNO(3) in humid N(2) at a controlled relative humidity (RH) between 20-90%. For comparison, similar studies were carried out using a similar crystal without the SAM coating. Changes in the surface were followed using Fourier transform infared spectroscopy (FTIR). In the case of the SAM-coated crystal, molecular HNO(3) and smaller amounts of NO(3)(-) ions were observed on the surface upon exposure to dry HNO(3). Addition of water vapor led to less molecular HNO(3) and more H(3)O(+) and NO(3)(-) complexed to water, but surprisingly, molecular HNO(3) was still evident in the spectra up to 70% RH. This suggests that part of the HNO(3) observed was initially trapped in pockets within the SAM and shielded from water vapor. After increasing the RH to 90% and then exposing the film to a flow of dry N(2), molecular nitric acid was regenerated, as expected from recombination of protons and nitrate ions as water evaporated. The nitric acid ultimately evaporated from the film. On the other hand, exposure of the SAM to HNO(3) and H(2)O simultaneously gave only hydronium and nitrate ions. Molecular dynamics simulations of defective SAMs in the presence of HNO(3) and water predict that nitric acid intercalates in defects as a complex with a

  9. A role of HNO3 on transparent conducting film with single-walled carbon nanotubes.

    PubMed

    Shin, Dong-Wook; Lee, Jong Hak; Kim, Yu-Hee; Yu, Seong Man; Park, Seong-Yong; Yoo, Ji-Beom

    2009-11-25

    There is some controversy regarding the effects of HNO3 on films of single-walled carbon nanotubes (SWCNTs). In this study we examined the change in sheet resistance of an HNO3-modified SWCNT film after different drying times at 85 degrees C using various analytical techniques. The shift and suppression in the Raman spectra, bleaching of the transition peaks related to van Hove singularities and a shift in the original peak in the C 1s XPS spectra provided evidence for p-type doping. A decrease in sheet resistance was also observed in the SWCNTs films due to the removal of residual N-methylpyrrolidone solvent on the surface and bundle of SWCNTs. These results suggest that p-type doping has a larger effect on the sheet resistance than the removal of residual N-methylpyrrolidone by an HNO3 treatment.

  10. Influence of monolayer amounts of HNO3 on the evaporation rate of H2O over ice in the range 179 to 208 K: a quartz crystal microbalance study.

    PubMed

    Delval, Christophe; Rossi, Michel J

    2005-08-18

    The evaporation flux J(ev) of H2O from thin H2O ice films containing between 0.5 and 7 monolayers of HNO3 has been measured in the range 179 to 208 K under both molecular and stirred flow conditions in isothermal experiments. FTIR absorption of the HNO3/H2O condensate revealed the formation of metastable alpha-NAT (HNO(3).3H2O) converting to stable beta-NAT at 205 K. After deposition of HNO3 for 16-80 s on a 1 mum thick pure ice film at a deposition rate in the range (6-60) x 10(12) molecules s(-1) the initial evaporative flux J(ev)(H2O) was always that of pure ice. J(ev)(H2O) gradually decreased with the evaporation of H2O and the concomitant increase of the average mole fraction of HNO3, chi(HNO3), indicating the presence of an amorphous mixture of H2O/HNO3 that is called complexed or (c)-ice whose vapor pressure is that of pure ice. The final value of J(ev) was smaller by factors varying from 2.7 to 65 relative to pure ice. Depending on the doping conditions and temperature of the ice film the pure ice thickness d(D) of the ice film for which J(ev) < 0.85J(ev)(pure ice) varied between 130 and 700 nm compared to the 1000 nm thick original ice film at 208 and 191 K, respectively, in what seems to be an inverse temperature dependence. There exist three different types of H2O molecules under the present experimental conditions, namely (a) free H2O corresponding to pure ice, (b) complexed H2O or c-ice, and (c) H2O molecules originating from the breakup of NAT or amorphous H2O/HNO3 mixtures. The significant decrease of J(ev)(H2O) with increasing chi(HNO3) leads to an increase of the evaporative lifetime of atmospheric ice particles in the presence of HNO3 and may help explain the occurrence of persistent and/or large contaminated ice particles at certain atmospheric conditions.

  11. Uptake of HNO3 to Deliquescent Sea-Salt and Mineral Dust Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Guimbaud, C.; Vlassenko, A.; Gaggeler, H.; Ammann, M.

    2002-12-01

    Uptake of HNO3 to aerosol particles is an important removal pathway of nitrogen oxides in the troposphere. Uptake of HNO3 to deliquescent sea-salt aerosol particles was studied in an aerosol flow reactor. Submicron sea-salt particles were used to avoid diffusion limitation in the gas-phase at atmospheric pressure. To overcome the sensitivity problems associated with low amount of reactants processed in such low aerosol masses, we used the short-lived radioactive tracer 13N to label the trace gas molecules at very low concentration. Uptake of HNO3 to deliquescent sea-salt particles was studied under a wide range of HNO3 concentration. Between 1 and 60 ppbv, the uptake coefficient was constant at 0.5+/-0.2 within the first few seconds, whereas at higher concentrations of about 600ppbv, the uptake coefficient rapidly dropped to 0.1 after about 1 second. This drop was due to complete release of chloride as HCl. The equilibrium conditions for these experiments were explored using the North American Aerosol Inorganics (AIM) model, which accounts for the activities of the concentrated solution of the deliquescent aerosol. It is concluded that the rates of uptake at low concentration were limited by the mass accommodation coefficient as both the diffusion in the liquid phase or the rate of release of HCl were not rate limiting. Using an identical approach, we started to investigate the uptake of HNO3 to mineral dust aerosol particles in a similar flow reactor, and first results will be presented. References Ammann, M, Using 13N as tracer in heterogeneous atmospheric chemistry experiments, Radiochim. Acta., 89, 831-838, 2001 Guimbaud, C., F., Arens, L., Gutzwiller, H.W, Gäggeler, and M. Ammann, Uptake of HNO3 to Deliquescent Sea-Salt Aerosol Particles, Atmos. Chem. Phys. Discuss., 2, 739-763, 2002

  12. Establishing a long-term, global stratospheric HNO3 data record combining UARS MLS with Aura MLS data by means of ground-based measurements

    NASA Astrophysics Data System (ADS)

    Fiorucci, I.; Muscari, G.; Froidevaux, L.; Santee, M. L.; de Zafra, R. L.

    2009-12-01

    Nitric Acid (HNO3) is a major player in processes controlling stratospheric ozone depletion. It is a primary reservoir for reactive nitrogen in the stratosphere and has a key role in both the activation and the deactivation of chlorine and bromine species. Since 1993 HNO3 observations have been carried out by means of a Ground-Based Millimeter-wave Spectrometer (GBMS) from a variety of sites in both hemispheres, at polar and mid-latitudes. The GBMS observes a cluster of weak emission lines centered at 269 GHz, with a pass band of 600 MHz and a resolution of 1 MHz. The retrieval of vertical profiles from the pressure-blended multiple line spectra is carried out with an Optimal Estimation Method. The GBMS provides HNO3 profiles from ~15 up to 50 km, with a vertical resolution of 6-8 km and a total uncertainty of ~15%. GBMS HNO3 measurements have been used within GOZCARDS (Global Ozone Chemistry and Related Trace gas Data Records for the Stratosphere), a multi-year MEaSUREs project, aimed at developing a long-term, commonly-formatted Earth system data record (ESDR) of stratospheric constituents relevant to the issues of ozone decline and expected recovery. This data record is based mainly on satellite-derived measurements. Nevertheless, ground-based observations can be critically used for assessing offsets between satellite data sets, as well as to fill gaps in temporal coverage when possible. Since the GBMS has been operated for more than 15 years (with minor instrumental upgrading), the GBMS HNO3 data record is well-suited for the GOZCARDS objectives; it offers a unique opportunity for the cross-calibration of HNO3 measurements from the NASA/JPL Microwave Limb Sounder (MLS) experiments (aboard the Upper Atmosphere Research Satellite (UARS) from 1991 to 1999, and on the Earth Observing System (EOS) Aura mission from 2004 to date). In this study we compare Aura MLS observations and GBMS HNO3 measurements obtained from the Italian Alpine station of Plateau Rosa, during

  13. HNO3 and HCl amounts over McMurdo during the spring of 1987

    NASA Technical Reports Server (NTRS)

    Murcray, Frank J.; Goldman, Aaron; Blatherwick, Ronald; Matthews, Andrew; Jones, Nicholas

    1989-01-01

    Infrared solar spectra were obtained from the ground at McMurdo, Antarctica, during September and October 1987. Absorption features due to HNO3 and HCl have been analyzed to determine the vertical column content of these compounds for the days when observations were made. The variation of these column amounts with time is presented and discussed.

  14. Observations of total RONO2 over the boreal forest: NOx sinks and HNO3 sources

    NASA Astrophysics Data System (ADS)

    Browne, E. C.; Min, K.-E.; Wooldridge, P. J.; Apel, E.; Blake, D. R.; Brune, W. H.; Cantrell, C. A.; Cubison, M. J.; Diskin, G. S.; Jimenez, J. L.; Weinheimer, A. J.; Wennberg, P. O.; Wisthaler, A.; Cohen, R. C.

    2013-01-01

    In contrast with the textbook view of remote chemistry where HNO3 formation is the primary sink of nitrogen oxides, recent theoretical analyses show that formation of RONO2 (ΣANs) from isoprene and other terpene precursors is the primary net chemical loss of nitrogen oxides over the remote continents where the concentration of nitrogen oxides is low. This then increases the prominence of questions concerning the chemical lifetime and ultimate fate of ΣANs. We present observations of nitrogen oxides and organic molecules collected over the Canadian boreal forest during the summer that show that ΣANs account for ~ 20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO3. This confirms the primary role of reactions producing ΣANs as a control over the lifetime of NOx (NOx = NO + NO2) in remote, continental environments. However, HNO3 is generally present in larger concentrations than ΣANs indicating that the atmospheric lifetime of ΣANs is shorter than the HNO3 lifetime. We investigate a range of proposed loss mechanisms that would explain the inferred lifetime of ΣANs finding that in combination with deposition, two processes are consistent with the observations: (1) rapid ozonolysis of isoprene nitrates where at least ~ 40% of the ozonolysis products release NOx from the carbon backbone and/or (2) hydrolysis of particulate organic nitrates with HNO3 as a product. Implications of these ideas for our understanding of NOx and NOy budget in remote and rural locations are discussed.

  15. Observations of total RONO2 over the boreal forest: NOx sinks and HNO3 sources

    NASA Astrophysics Data System (ADS)

    Browne, E. C.; Min, K.-E.; Wooldridge, P. J.; Apel, E.; Blake, D. R.; Brune, W. H.; Cantrell, C. A.; Cubison, M. J.; Diskin, G. S.; Jimenez, J. L.; Weinheimer, A. J.; Wennberg, P. O.; Wisthaler, A.; Cohen, R. C.

    2013-05-01

    In contrast with the textbook view of remote chemistry where HNO3 formation is the primary sink of nitrogen oxides, recent theoretical analyses show that formation of RONO2 (ΣANs) from isoprene and other terpene precursors is the primary net chemical loss of nitrogen oxides over the remote continents where the concentration of nitrogen oxides is low. This then increases the prominence of questions concerning the chemical lifetime and ultimate fate of ΣANs. We present observations of nitrogen oxides and organic molecules collected over the Canadian boreal forest during the summer which show that ΣANs account for ~20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO3. This confirms the primary role of reactions producing ΣANs as a control over the lifetime of NOx (NOx = NO + NO2) in remote, continental environments. However, HNO3 is generally present in larger concentrations than ΣANs indicating that the atmospheric lifetime of ΣANs is shorter than the HNO3 lifetime. We investigate a range of proposed loss mechanisms that would explain the inferred lifetime of ΣANs finding that in combination with deposition, two processes are consistent with the observations: (1) rapid ozonolysis of isoprene nitrates where at least ~40% of the ozonolysis products release NOx from the carbon backbone and/or (2) hydrolysis of particulate organic nitrates with HNO3 as a product. Implications of these ideas for our understanding of NOx and NOy budget in remote and rural locations are discussed.

  16. Gas phase spectroscopy of HNO3 in the region 2000-8500 cm(-1).

    PubMed

    Feierabend, K J; Havey, D K; Vaida, V

    2004-10-01

    Spectra of gas phase HNO3 were collected in the region 2000-8500 cm(-1) using Fourier-transform infrared spectroscopy. This region is dominated by the nu1 O-H stretching mode but also contains many previously unreported combination bands and overtones. This work marks the first observation of Fermi resonance the 2nu1 O-H stretching overtone. Previously unobserved bands were assigned and integrated intensities were obtained. For bands already reported in the literature, comparisons of relative intensities are presented when possible. This work gives a brief discussion on the trends in overtone intensities and on mode mixing in HNO3 in relation to previous experimental and theoretical studies.

  17. Stratospheric H2O and HNO3 profiles derived from solar occultation measurements

    NASA Astrophysics Data System (ADS)

    Fischer, H.; Fergg, F.; Rabus, D.; Burkert, P.

    1985-04-01

    Compact two-channel radiometers for solar occultation experiments have been constructed in order to measure stratospheric trace gases. The instruments can be used as filter- or correlation-type radiometers, depending on the trace gas under investigation. Within the LIMS correlative measurement program, balloon flights were performed with a payload of up to four of these two-channel radiometers. From the filter-type measurements, profiles of the trace gases H2O and HNO3 are inferred for the height region between the tropopause and the balloon float level. The data evaluation also includes a comprehensive analysis of the error sources and their effect on the accuracy of the trace gas profiles. The derived H2O and HNO3 profiles are assessed against the observations of other authors and are discussed in the light of the trace gas distributions calcualted from photochemical models.

  18. The transport of atmospheric NOx and HNO3 over Cape Town

    NASA Astrophysics Data System (ADS)

    Abiodun, B. J.; Ojumu, A. M.; Jenner, S.; Ojumu, T. V.

    2014-01-01

    Cape Town, the most popular tourist city in Africa, usually experiences air pollution with unpleasant odour in winter. Previous studies have associated the pollution with local emission of pollutants within the city. The present study examines the transport of atmospheric pollutants (NOx and HNO3) over South Africa and shows how the transport of pollutants from the Mpumalanga Highveld, a major South African industrial area, may contribute to the pollution in Cape Town. The study analysed observation data (2001-2008) from the Cape Town air-quality network and simulation data (2001-2004) from a regional climate model (RegCM) over southern Africa. The simulation accounts for the influence of complex topography, atmospheric conditions, and atmospheric chemistry on emission and transport of pollutants over southern Africa. Flux budget analysis was used to examine whether Cape Town is a source or sink for NOx and HNO3 during the extreme pollution events. The results show that extreme pollution events in Cape Town are associated with the lower level (surface - 850 hPa) transport of NOx from the Mpumalanga Highveld to Cape Town, and with a tongue of high concentration of HNO3 that extends from the Mpumalanga Highveld to Cape Town along the south coast of South Africa. The prevailing atmospheric conditions during the extreme pollution events feature an upper-level (700 hPa) anticyclone over South Africa and a lower-level col over Cape Town. The anticyclone induces a strong subsidence motion, which prevents vertical mixing of the pollutants and caps high concentration of pollutants close to the surface as they are transported from the Mpumalanga Highveld toward Cape Town. The col accumulates the pollutants over the city. This study shows that Cape Town can be a sink for the NOx and HNO3 during extreme pollution events and suggests that the accumulation of pollutants transported from other areas (e.g. the Mpumalanga Highveld) may contribute to the air pollution in Cape Town.

  19. Coupled Variations in HNO3 and Soluble Gas Phase Chloride in the Houston Region

    NASA Astrophysics Data System (ADS)

    Dibb, J. E.; Corr, C. A.; Lefer, B. L.; Flynn, J. H.

    2010-12-01

    The University of New Hampshire mist chamber/ion chromatography (MC/IC) system was operated on the north Moody Tower as part of the Study of Houston Atmospheric and Radical Precursors (SHARP) during April-May, 2009. The MC/IC system provided 5-minute resolution measurements of HONO, HNO3, and soluble gas phase chloride (soluble Cl-) throughout the intensive campaign. Several other papers in this session discuss the HONO results, here we focus on HNO3, and soluble Cl-. These gases were highly correlated on short (minutes to hours time scales) throughout the SHARP campaign but anticorrelated when binned by broad wind direction sectors. Peak mixing ratios of HNO3, occurred during transport from the north and east and minima were observed under southerly flow, with the opposite true for soluble Cl-, yet strong correlation from sample to sample and diurnally were observed regardless of wind direction. It should be noted that the mixing ratios of soluble Cl- are substantial in Houston. Even during intervals with sustained northerly flow (relatively low Cl-) daytime maxima routinely exceeded 1 ppbv. Similar observations made during TexAQS 2006 on the Moody Tower and the NOAA vessel Ronald H Brown indicate that abundant soluble Cl-, linked with HNO3, by processes not yet understood, is characteristic of the Houston-Galveston Bay region during both spring and summer. Limited data on bulk aerosol composition at Moody Tower suggest that displacement of HCl from sea salt is not sufficient to account for all of the soluble Cl- observed in Houston.

  20. Simulations of the Vertical Redistribution of HNO3 by NAT or NAD PSCs: The Sensitivity to the Number of Cloud Particles Formed and the Cloud Lifetime

    NASA Technical Reports Server (NTRS)

    Jensen, Eric J.; Tabazadeh, Azadeh; Drdla, Katja; Toon, Owen B.; Gore, Warren J. (Technical Monitor)

    2000-01-01

    Recent satellite and in situ measurements have indicated that limited denitrification can occur in the Arctic stratosphere. In situ measurements from the SOLVE campaign indicate polar stratospheric clouds (PSCs) composed of small numbers (about 3 x 10^ -4 cm^-3) of 10-20 micron particles (probably NAT or NAD). These observations raise the issue of whether low number density NAT PSCs can substantially denitrify the air with reasonable cloud lifetimes. In this study, we use a one dimensional cloud model to investigate the verticle redistribution of HNO3 by NAT/NAD PSCs. The cloud formation is driven by a temperature oscillation which drops the temperature below the NAT/NAD formation threshold (about 195 K) for a few days. We assume that a small fraction of the available aerosols act as NAT nuclei when the saturation ratio of HNO3 over NAT(NAD) exceeds 10(l.5). The result is a cloud between about 16 and 20 km in the model, with NAT/NAD particle effective radii as large as about 10 microns (in agreement with the SOLVE data). We find that for typical cloud lifetimes of 2-3 days or less, the net depletion of HNO3 is no more than 1-2 ppbv, regardless of the NAT or NAD particle number density. Repeated passes of the air column through the cold pool build up the denitrification to 3-4 ppbv, and the cloud altitude steadily decreases due to the downward transport of nitric acid. Increasing the cloud lifetime results in considerably more effective denitrification, even with very low cloud particle number densities. As expected, the degree of denitrification by NAT clouds is much larger than that by NAD Clouds. Significant denitrification by NAD Clouds is only possible if the cloud lifetime is several days or more. The clouds also cause a local maximum HNO3 mixing ratio at cloud base where the cloud particles sublimate.

  1. Composition-dependent freezing nucleation rates for HNO3/H2O aerosols resembling gravity-wave-perturbed stratospheric particles

    NASA Astrophysics Data System (ADS)

    Prenni, Anthony J.; Onasch, Timothy B.; Tisdale, Robert T.; Siefert, Ronald L.; Tolbert, Margaret A.

    1998-11-01

    Laboratory measurements are presented for the freezing kinetics of H2O/HNO3 aerosols over the temperature range of 188-204 K. For 2:1 H2O:HNO3 aerosols crystallizing to NAD we observed a maximum nucleation rate of J = 9.3×109 cm-3 s-1 at 194 K. This temperature is between the glass point of 161 K [Ji et al., 1993] and the melting point of 235.5 K [Ji et al., 1996]. This can be compared to a previous measurement of J = 6.7×109 cm-3 s-1 at 193 K [Disselkamp et al., 1996] and lower temperature measurements of J ≈ 1010-1012 cm-3 s-1 at 178.8 - 175.8 K [Bertram and Sloan, 1998a]. Measured nucleation rates decrease as the aerosol becomes dilute, but NAD formation is still observable for 2.5:1 H2O:HNO3 at temperatures near 195 K. In contrast, freezing of 3:1 H2O:HNO3 aerosol was not observed for constant temperature experiments throughout this temperature range, yielding an upper limit of J<1.5×109 cm-3 s-1. This is the lowest experimental value determined for 3:1 H2O:HNO3 freezing rates at these temperatures. From the measured freezing rates and knowledge of the free energy of diffusion the average interfacial free energy for NAD in a 2:1 H2O:HNO3 solution was determined to be σ = 25.2 ergs cm-2. A limit for the interfacial free energy was placed on 3:1 H2O:HNO3 particles, for which freezing was not observed. These data imply that if aerosols reach compositions more concentrated than 3:1 H2O:HNO3 in the atmosphere, NAD may play a role in polar stratospheric cloud formation.

  2. Evidence that nitric acid increases relative humidity in low-temperature cirrus clouds.

    PubMed

    Gao, R S; Popp, P J; Fahey, D W; Marcy, T P; Herman, R L; Weinstock, E M; Baumgardner, D G; Garrett, T J; Rosenlof, K H; Thompson, T L; Bui, P T; Ridley, B A; Wofsy, S C; Toon, O B; Tolbert, M A; Kärcher, B; Peter, Th; Hudson, P K; Weinheimer, A J; Heymsfield, A J

    2004-01-23

    In situ measurements of the relative humidity with respect to ice (RHi) and of nitric acid (HNO3) were made in both natural and contrail cirrus clouds in the upper troposphere. At temperatures lower than 202 kelvin, RHi values show a sharp increase to average values of over 130% in both cloud types. These enhanced RHi values are attributed to the presence of a new class of HNO3-containing ice particles (Delta-ice). We propose that surface HNO3 molecules prevent the ice/vapor system from reaching equilibrium by a mechanism similar to that of freezing point depression by antifreeze proteins. Delta-ice represents a new link between global climate and natural and anthropogenic nitrogen oxide emissions. Including Delta-ice in climate models will alter simulated cirrus properties and the distribution of upper tropospheric water vapor.

  3. Investigation of catalytic reduction and filter techniques for simultaneous measurements of NO, NO2, and HNO3 in the stratosphere

    NASA Technical Reports Server (NTRS)

    Wendt, J.; Fabian, Peter; Flentje, G.; Kourtidis, K.

    1994-01-01

    A concept for measuring stratospheric NOy-species is presented which utilizes the catalytic reduction of NO2 and HNO3 over heated metal catalysts and the chemisorption of HNO3 on Nylon. Using the Max Planck Institute for Aeronomy (MPAE) chemiluminescent balloon-borne sonde, stratospheric NO and NO2 profiles have been measured since 1983. NO is detected by chemiluminescence produced in reaction with O3 while NO2 needs first to be converted to NO over a heated stainless steel catalyst. To improve this technique for simultaneously measuring HNO3, the catalytic reduction of NO2 and HNO3 over several metal catalysts and the chemisorption of NO2 and HNO3 on Nylon have been investigated in laboratory tests. The results of these tests under simulated stratospheric conditions are presented in detail in this paper. They demonstrate that the simultaneous measurement of NO, NO2 and HNO3 is indeed possible with the combination of stainless steel or Au as a catalyst and a nylon filter.

  4. Growth of nitric acid hydrates on thin sulfuric acid films

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Middlebrook, Ann M.; Wilson, Margaret A.; Tolbert, Margaret A.

    1994-01-01

    Type I polar stratospheric clouds (PSCs) are thought to nucleate and grow on stratospheric sulfate aerosols (SSAs). To model this system, thin sulfuric acid films were exposed to water and nitric acid vapors (1-3 x 10(exp -4) Torr H2O and 1-2.5 x 10(exp -6) Torr HNO3) and subjected to cooling and heating cycles. Fourier Transform Infrared (FTIR) spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films that condensed. Nitric acid trihydrate (NAT) was observed to grow on crystalline sulfuric acid tetrahydrate (SAT) films. NAT also condensed in/on supercooled H2SO4 films without causing crystallization of the sulfuric acid. This growth is consistent with NAT nucleation from ternary solutions as the first step in PSC formation.

  5. Heat-Exchange Fluids for Sulfuric Acid Vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1982-01-01

    Some fluorine-substituted organic materials meet criteria for heat-exchange fluids in contact with sulfuric acid. Most promising of these are perfluoropropylene oxide polymers with degree of polymerization (DP) between 10 and 50. It is desirable to have DP in high range because vapor pressure of material decreases as DP increases, and high-DP liquids have lower loss due to vaporization.

  6. Condensation of acetol and acetic acid vapor with sprayed liquid

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A cellulose-derived fraction of biomass pyrolysis vapor was simulated by evaporating acetol and acetic acid (AA) from flasks on a hot plate. The liquid in the flasks was infused with heated nitrogen. The vapor/nitrogen stream was superheated in a tube oven and condensed by contact with a cloud of ...

  7. Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  8. Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  9. The determination of HNO3 column amounts from tunable diode laser heterodyne spectrometer spectra taken at Jungfruajoch, Switzerland

    NASA Technical Reports Server (NTRS)

    Fogal, P. F.; Murcray, D. G.; Martin, N. A.; Swann, N. R.; Woods, P. T.; Mcelroy, C. T.

    1994-01-01

    In May of 1991 a tunable diode laser heterodyne spectrometer built by the National Physical Laboratory was operated at the International Scientific Station of the Jungfraujoch (46.5 deg N, 8.0 deg E, altitude 3.56 km). Nitric acid spectra in the region of 868 wavenumbers were recorded at sunset and sunrise on two separate days at a resolution of 0.0013 wavenumbers with a signal-to-noise ratio of approximately 130:1. A vertical column amount of HNO3 of 1.61 x 10(exp 16) molecules/sq cm was determined using an atmospheric transmission model developed at the University of Denver. The mean of a number of mid-latitude, northern hemisphere profiles was used as the initial profile for the inversion. A comparison of different initial profiles provides information on the sensitivity of the retrieved column amount of 1.61 x 10(exp 16) molecules/sq cm lies within the range of values published in the World Meteorological Organization Report no. 16 (1986), but is considerably larger than the value of (0.99 - 1.29) x 10(exp 16) reported by Rinsland et al. (1991) for June during the period 1986 to 1990.

  10. The effect of HNO3 on morphology, phase transformation, and luminescence properties of LaPO4:Eu3+ phosphors

    NASA Astrophysics Data System (ADS)

    Zhou, Ruisen; Lv, Meng; Li, Xia

    2016-01-01

    LaPO4:Eu3+ powders with different morphologies were hydrothermally constructed by adjusting the amount of HNO3 without using a catalyst, surfactant, or template. The as-prepared products were characterized by photoluminescence spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), infrared (IR) spectra, and X-ray photoelectron spectroscopy. The SEM study revealed that the amount of HNO3 played a crucial role in the morphology of the final products. The XRD results indicated that the as-prepared samples were in the monoclinic phase when 3 mL of HNO3 was used. The HR-TEM micrographs and SAED results demonstrated that the prepared nanorods were single and crystalline in nature with HNO3, and that they grew preferentially along the [0 1 2] direction. The emission spectra showed that the LaPO4:Eu3+ samples had the strongest emission intensity when prepared with HNO3.

  11. Determination of total fluoride in HF/HNO3/H2SiF6 etch solutions by new potentiometric titration methods.

    PubMed

    Weinreich, Wenke; Acker, Jörg; Gräber, Iris

    2007-03-30

    In the photovoltaic industry the etching of silicon in HF/HNO(3) solutions is a decisive process for cleaning wafer surfaces or to produce certain surface morphologies like polishing or texturization. With regard to cost efficiency, a maximal utilisation of etch baths in combination with highest quality and accuracy is strived. To provide an etch bath control realised by a replenishment with concentrated acids the main constituents of these HF/HNO(3) etch solutions including the reaction product H(2)SiF(6) have to be analysed. Two new methods for the determination of the total fluoride content in an acidic etch solution based on the precipitation titration with La(NO(3))(3) are presented within this paper. The first method bases on the proper choice of the reaction conditions, since free fluoride ions have to be liberated from HF and H(2)SiF(6) at the same time to be detected by a fluoride ion-selective electrode (F-ISE). Therefore, the sample is adjusted to a pH of 8 for total cleavage of the SiF(6)(2-) anion and titrated in absence of buffers. In a second method, the titration with La(NO(3))(3) is followed by a change of the pH-value using a HF resistant glass-electrode. Both methods provide consistent values, whereas the analysis is fast and accurate, and thus, applicable for industrial process control.

  12. Acetic acid vapor levels associated with facial prosthetics

    SciTech Connect

    McElroy, T.H.; Guerra, O.N.; Lee, S.A.

    1985-01-01

    The use of Silastic Medical Adhesive Type A in the fabrication of facial prostheses may cause health hazards to the patient and the operator because of acetic acid emissions. Caution must be exercised to remove acetic acid vapors from the air and unliberated acetic acid from material applied directly to the skin.

  13. Modified HNO3 seasonality in volcanic layers of a polar ice core - Snow-pack effect or photochemical perturbation?

    NASA Technical Reports Server (NTRS)

    Laj, Paolo; Palais, Julie M.; Gardner, James E.; Sigurdsson, Haraldur

    1993-01-01

    Changes in atmospheric HNO3 chemistry following the Laki (1783), Tambora (1815), and Katmai (1912) volcanic eruptions are presently investigated in view of a central Greenland ice core's chemical composition. Attention is given to the concentration of several cations and anions, using ion chromatography. Following the eruptions, the ratio of winter to summer depositions of NO3(-) was significantly higher than during nonvolcanic periods. While this may be due to ice pack effects, it is proposed that large concentrations of the stratospheric H2SO4 particles ejected by the volcanoes favored HNO3 removal during Arctic winter.

  14. Potential heat exchange fluids for use in sulfuric acid vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1979-01-01

    A series of perhalocarbons are proposed as candidate heat exchange fluids for service in thermochemical cycles for hydrogen production that involve direct contact of the fluid with sulfuric acid and vaporization of the acid. The required chemical and physical criteria of the liquids are described and the results of some preliminary high temperature test data are presented.

  15. Spectrometric analysis of process etching solutions of the photovoltaic industry--determination of HNO3, HF, and H2SiF6 using high-resolution continuum source absorption spectrometry of diatomic molecules and atoms.

    PubMed

    Bücker, Stefan; Acker, Jörg

    2012-05-30

    The surface of raw multicrystalline silicon wafers is treated with HF-HNO(3) mixtures in order to remove the saw damage and to obtain a well-like structured surface of low reflectivity, the so-called texture. The industrial production of solar cells requires a consistent level of texturization for tens of thousands of wafers. Therefore, knowing the actual composition of the etch bath is a key element in process control in order to maintain a certain etch rate through replenishment of the consumed acids. The present paper describes a novel approach to quantify nitric acid (HNO(3)), hydrofluoric acid (HF), and hexafluosilicic acid (H(2)SiF(6)) using a high-resolution continuum source graphite furnace absorption spectrometer. The concentrations of Si (via Si atom absorption at the wavelength 251.611 nm, m(0),(Si)=130 pg), of nitrate (via molecular absorption of NO at the wavelength 214.803 nm, [Formula: see text] ), and of total fluoride (via molecular absorption of AlF at the wavelength 227.46 nm, m(0,F)=13 pg) were measured against aqueous standard solutions. The concentrations of H(2)SiF(6) and HNO(3) are directly obtained from the measurements. The HF concentration is calculated from the difference between the total fluoride content, and the amount of fluoride bound as H(2)SiF(6). H(2)SiF(6) and HNO(3) can be determined with a relative uncertainty of less than 5% and recoveries of 97-103% and 96-105%, respectively. With regards to HF, acceptable results in terms of recovery and uncertainty are obtained for HF concentrations that are typical for the photovoltaic industry. The presented procedure has the unique advantage that the concentration of both, acids and metal impurities in etch solutions, can be routinely determined by a single analytical instrument.

  16. Global sensitivity of aviation NOx effects to the HNO3-forming channel of the HO2 + NO reaction

    NASA Astrophysics Data System (ADS)

    Gottschaldt, K.; Voigt, C.; Jöckel, P.; Righi, M.; Deckert, R.; Dietmüller, S.

    2013-03-01

    The impact of a recently proposed HNO3-forming channel of the HO2 + NO reaction on atmospheric ozone, methane and their precursors is assessed with the aim to investigate its effects on aviation NOx induced radiative forcing. The first part of the study addresses the differences in stratospheric and tropospheric HOx-NOx chemistry in general, by comparing a global climate simulation without the above reaction to two simulations with different rate coefficient parameterizations for HO2 + NO → HNO3. A possible enhancement of the reaction by humidity, as found by a laboratory study, particularly reduces the oxidation capacity of the atmosphere, increasing methane lifetime significantly. Since methane lifetime is an important parameter for determining global methane budgets, this might affect estimates of the anthropogenic greenhouse effect. In the second part aviation NOx effects are isolated independently for each of the three above simulations. Warming and cooling effects of aircraft NOx emissions are both enhanced when considering the HNO3-forming channel, but the sum is shifted towards negative radiative forcing. Uncertainties associated with the inclusion of the HO2 + NO → HNO3 reaction and with its corresponding rate coefficient propagate a considerable additional uncertainty on estimates of the climate impact of aviation and on NOx-related mitigation strategies.

  17. Infrared studies of sulfuric acid and its impact on polar and global ozone

    NASA Astrophysics Data System (ADS)

    Iraci, Laura Tracy

    Sulfuric acid aerosols are present throughout the lower stratosphere and play an important role in both polar and global ozone depletion. In the polar regions, stratospheric sulfate aerosols (SSAs) act as nuclei for the growth of polar stratospheric clouds (PSCs). Heterogeneous reactions can occur on these PSCs, leading to chlorine activation and catalytic ozone destruction. This thesis addresses the issue of polar ozone depletion through laboratory studies which examine the nucleation of PSCs on sulfuric acid. In addition, chemistry which occurs directly on sulfate aerosols may impact ozone at midlatitudes, and studies describing one such reaction are presented as well. To study the growth of type I PSCs on sulfuric acid, thin H2SO4 films were exposed to water and nitric acid vapors at stratospheric temperatures. Fourier transform infrared spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films which condensed. Supercooled liquid sulfuric acid films showed uptake of HNO3 to form ternary solutions, followed by crystallization of nitric acid trihydrate (NAT). When crystalline sulfuric acid tetrahydrate (SAT) films were exposed to nitric acid and water, condensation of a supercooled HNO3/H2O layer was often observed. As predicted by theory, some of the SAT crystal then dissolved, creating a ternary H2SO4/HNO3/H2O solution. From this solution, NAT nearly always crystallized, halting the phase change of sulfuric acid. If a supercooled nitric acid layer did not condense on frozen sulfuric acid, crystalline NAT was not deposited from the gas phase when SNAT/leq41. At significantly higher supersaturations, NAT could be forced to condense on sulfuric acid, regardless of its phase. Calculations of the contact parameter from experimental data indicate that m<0.79 for NAT on SAT, predicting a significant barrier to nucleation of NAT from the gas phase. While PSCs can form only in the cold polar regions of the stratosphere, sulfuric

  18. Temperature dependences of saturated vapor pressure and the enthalpy of vaporization of n-pentyl esters of dicarboxylic acids

    NASA Astrophysics Data System (ADS)

    Portnova, S. V.; Krasnykh, E. L.; Levanova, S. V.

    2016-05-01

    The saturated vapor pressures and enthalpies of vaporization of n-pentyl esters of linear C2-C6 dicarboxylic acids are determined by the transpiration method in the temperature range of 309.2-361.2 K. The dependences of enthalpies of vaporization on the number of carbon atoms in the molecule and on the retention indices have been determined. The predictive capabilities of the existing calculation schemes for estimation of enthalpy of vaporization of the studied compounds have been analyzed.

  19. Modification of active and porous sublayers of aged polyamide/polysulfone composite membranes due to HNO3 treatment: effect of treatment time.

    PubMed

    Benavente, J; Vázquez, M I; de Lara, R

    2006-05-01

    Changes in electrical and transport parameters for aged composite polyamide/polysulfone membrane samples (PAC) and their porous support layers (PSU) as a result of chemical treatment (immersion in 1 M HNO3 solution) at four different times (12 h < or = t < or = 72 h) have been obtained. Salt permeability, ion transport number, and membrane electrical resistance for the treated samples were determined from salt diffusion, membrane potential, and impedance spectroscopy measurements, which were carried out with the membranes in contact with NaCl solutions at different concentrations and compared with those determined for fresh and aged nontreated samples. Results show the strong effect of aging on membrane parameters, particularly the decrease in salt permeability (P(s)) and the increase in membrane electrical resistance (R(m)), while ion transport number is hardly affected by aging, chemical treatment, or treatment time. Results show how the compaction of the porous structure causes by aging (dried membrane matrix structure) can be partially reduced by HNO3 treatment, and they also allow the estimation of 24-h treatment as the optimum time (higher salt permeability and lower membrane electrical resistance), mainly for the polysulfone support layer. The use of equivalent circuits in the analysis of impedance spectroscopy data allows separate estimation of the electrical resistance associated with each sublayer of the composite PAC membrane samples. On the other hand, chemical changes in the active top layer of the PAC membrane (polyamide active layer) were obtained from XPS analysis, which show some modifications in the atomic concentration percentages of the polyamide characteristic elements as a result of acidic treatment time, which are more significant after 72-h acidic immersion.

  20. Potential heat exchange fluids for use in sulfuric acid vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1981-01-01

    A series of liquids have been screened as candidate heat exchange fluids for service in thermochemical cycles that involve the vaporization of sulfuric acid. The required chemical and physical criteria of the liquids is described with the results of some preliminary high temperature test data presented.

  1. Determination of trace elements in foods by HCl-HNO3 leaching and flame atomic absorption spectroscopy.

    PubMed

    Puchyr, R F; Shapiro, R

    1986-01-01

    Aluminum, iron, tin, zinc, calcium, magnesium, nickel, copper, chromium, cadmium, and potassium in foods can be extracted by HCl-HNO3 leaching and determined quantitatively using flame atomic absorption spectroscopy (AAS), with recoveries ranging from 90 to 110%. Thirty to 40 samples of almost any type of food sample can be analyzed routinely for 2 elements in 4-5 h. In contrast, one or 2 days are required when a wet-ash or dry-ash technique is used. Extraction consists of weighing 2-10 g samples into 125 mL Erlenmeyer flasks, adding 20 mL concentrated HCl-HNO3 (9 + 1), then heating in a 82- 93 degrees C water bath for 30 min. After cooling, samples are diluted to volume in 50 mL Nessler tubes and then filtered through No. 541 or 540 Whatman paper. The filtrate is analyzed directly by AAS.

  2. HNO3, N2O5 and CIONO2 Enhancements after the October-November 2003 Solar Proton Events

    NASA Technical Reports Server (NTRS)

    Lopez-Puertas, M.; Funke, B.; Gil-Lopez, S.; Tsidu, G. Mengistu; Fischer, H.; Jackman, C. H.

    2005-01-01

    The large solar storm in October-November 2003 produced enormous amounts of high-energy protons which reached the Earth and penetrated into the middle atmosphere in the polar regions. At this time, the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board the Environmental Satellite (ENVISAT) was observing the atmosphere in the 6-68 km altitude range. MIPAS observed significant enhancements of the NO(y) components HNO3, N2O5 and CIONO2 in the Northern polar stratosphere after the intense solar proton events. Two distinct HNO3 enhancements were observed. An instantaneous increase of 1-2 ppbv was observed immediately after the SPEs and is attributed to gas-phase chemistry: NO2 + OH + M yields HNO3 + M, accelerated by SPE-produced excess OH. A very large second increase of 1- 5 ppbv started around 10 November and lasted until the end of December. It is attributed to NO(x) (NO+NO2) produced in the mesosphere during the major SPEs in late October/early November and then transported downwards during November and December, partially converted to N2O5 in the upper stratosphere, which finally formed HNO3 via ion cluster reactions. N2O5 was observed to increase by 0.1-0.4 ppbv 1-3 days after the major SPEs and reached down to 30 km altitude. A second, more pronounced N2O5 enhancement of up to 1.2 ppbv at 40 km appeared about 12-13 days after the major SPEs. With a delay of 1-2 days after the major SPEs CIONO2 increased by up to 0.4 ppbv (40%) at 32 km altitude. NO(y) enhancements in the Southern hemisphere were generally less pronounced.

  3. Lifetime Extension of Cirrus Cloud Ice Particles upon Contamination with HCl and HNO3 under conditions of the Upper Troposphere and Lower Stratosphere

    NASA Astrophysics Data System (ADS)

    Rossi, Michel J.; Delval, Christophe

    2016-04-01

    Ice particles in the Upper Troposphere/Lower Stratosphere (UT/LS) are the seat of heterogeneous chemical processes that are important in polar ozone chemistry. Estimated evaporative lifetimes of typical pure ice particles of a few micrometers radius in Cirrus clouds are on the order of a minute or so at 80% relative humidity, too short to allow significant heterogeneous processing. We took this as a motivation to systematically measure absolute rates of evaporation and condensation of H2O in 1 to 2 micrometer thick ice films taken as proxies for small atmospheric ice particles under controlled conditions of HCl and HNO3 trace gas contamination. We have used a multidiagnostic reaction vessel equipped with residual gas mass spectrometry (MS), FTIR absorption spectroscopy in transmission and a quartz crystal microbalance (QCMB) in order to simultaneously observe both the gas and condensed phases under relevant atmospheric conditions. The rates (Rev(H2O)) or fluxes of evaporation (Jev(H2O)) of H2O from thin ice films contaminated by a measured amount of HCl in the range of 10% of a formal monolayer to 20 formal monolayers decreased by factors of between 2 and 50 depending on parameters such as temperature of deposition (Tdep), rate (RHCl) and dose (NHCl) of contaminant doping. Experiments with HCl fell into two categories as far as the decrease of Jev with the average mole fraction of contaminant (χHCl) in the remaining ice slab was concerned: one group where Jev(H2O) decreased gradually after pure ice evaporated, and another group where Jev(H2O) abruptly changes with χHCl after evaporation of excess ice. FTIR spectroscopy revealed an unknown, yet crystalline form of HCl hydrate upon HCl doping that does not correspond to a known crystalline hydrate. Of importance is the observation, that the equilibrium vapor pressure of these contaminated ices correspond to that of pure ice even after evaporation of excess ice at the characteristic rate of pure ice evaporation

  4. Coupled aerosol-chemical modeling of UARS HNO3 and N2O5 measurements in the Arctic upper stratosphere

    NASA Astrophysics Data System (ADS)

    Bekki, S.; Chipperfield, M. P.; Pyle, J. A.; Remedios, J. J.; Smith, S. E.; Grainger, R. G.; Lambert, A.; Kumer, J. B.; Mergenthaler, J. L.

    1997-04-01

    Gas-phase photochemical models do not account for the formation of a secondary altitude HNO3 maximum in the upper stratosphere at high latitudes during winter, suggesting that some processes are missing in the currently accepted chemistry of reactive nitrogen species [Kawa et al, 1995]. Heterogeneous chemistry on aerosol particles had been discounted as the cause because the aerosol surface area is expected to be very low at these altitudes. We have coupled a sulphate aerosol microphysical model to a chemical transport model to investigate this model deficiency in the Arctic during January 1992. The aerosol model predicts the formation of small sulphate particles at 1100 K. Comparisons with cryogenic limb array etalon spectrometer (CLAES) HNO3 and improved stratospheric and mesospheric sounder (ISAMS) N2O5 observations show that the heterogeneous conversion of N2O5 to HNO3 on the modeled small sulphate particles can account for some of the unexpected features seen in Upper Atmosphere Research Satellite (UARS) observations.

  5. Analysis of the ν 8+ ν 9Band of HNO 3, Line Positions and Intensities, and Resonances Involving the v6= v7= 1 Dark State

    NASA Astrophysics Data System (ADS)

    Perrin, A.; Flaud, J.-M.; Keller, F.; Goldman, A.; Blatherwick, R. D.; Murcray, F. J.; Rinsland, C. P.

    1999-03-01

    Using a high-resolution (R= 0.0025 cm-1) Fourier transform spectrum of nitric acid recorded at room temperature in the 1100-1240 cm-1region, it has been possible to perform a more extended analysis of the ν8+ ν9band of HNO3centered at 1205.7075 cm-1. As in a recent analysis of this band [W. F. Wang, P. P. Ong, T. L. Tan, E. C. Looi, and H. H. Teo,J. Mol. Spectrosc.183, 407-413 (1997)], the Hamiltonian used for the line positions calculation takes into account, for the upper state, the ΔK= ±2 anharmonic resonance linking the rotational levels of thev8=v9= 1 "bright" vibrational state and those of the "dark"v6=v7= 1 vibrational state. More than 4800 lines were assigned in the ν8+ ν9band, which involve significantly higher rotational quantum numbers than in previous works. On the other hand, and surprisingly as compared to previous studies, the ν8+ ν9band appears to be a hybrid band. In fact, nonnegligibleB-type transitions could be clearly identified among the much strongerA-type lines. Accordingly, a set of individual line intensities were measured for lines of both types and were introduced in a least-squares fit to get theA- andB-type components of the transition moment operator. Finally, a synthetic spectrum of the 8.3-μm region of HNO3has been generated, using for the line positions and line intensities the Hamiltonian constants and the expansion of the transition moment operator which were determined in this work. In this way, theB-type and theA-type components of the ν8+ ν9band appear to contribute for about {1}/{4} and {3}/{4}, respectively, to the total band intensity.

  6. Analysis of seasonal variation of stratospheric nitric acid

    NASA Astrophysics Data System (ADS)

    Gruzdev, A. N.

    1998-11-01

    Data from the draft COSPAR reference model for stratospheric nitric acid (HNO3) are analysed. Eight months of LIMS HNO3 measurements allow the analysis of dynamics of regimes associated with the annual HNO3 maximum followed by the HNO3 decrease in the Northern Hemisphere and the annual HNO3 minimum followed by the HNO3 increase in the Southern Hemisphere. The HNO3 minimum is noted earlier (in November) in the Southern Hemisphere subtropical upper stratosphere, from where the regime of minimum HNO3 values propagates to the southern high-latitude middle stratosphere, and then (in Austral summer) the equatorward propagation of the regime is observed, with a persistent downward component. The regime of the HNO3 annual maximum in the Northern Hemisphere propagates from the Arctic lower stratosphere (in autumn) and from the tropical middle stratosphere (in late summer), so that in the mid-latitude middle stratosphere the downward propagation of the regime is observed. Evolution of areas with HNO3 increase and decrease by 1 ppbv against the January HNO3 distribution quantifies intensity of the HNO3 decrease in winter-spring in the Northern Hemisphere and the HNO3 increase in Austral summer-autumn in the Southern Hemisphere.

  7. The mid-IR Absorption Cross Sections of α- and β-NAT (HNO3 · 3H2O) in the range 170 to 185 K and of metastable NAD (HNO3 · 2H2O) in the range 172 to 182 K

    NASA Astrophysics Data System (ADS)

    Iannarelli, R.; Rossi, M. J.

    2015-11-01

    Growth and Fourier transform infrared (FTIR) absorption in transmission of the title nitric acid hydrates have been performed in a stirred flow reactor (SFR) under tight control of the H2O and HNO3 deposition conditions affording a closed mass balance of the binary mixture. The gas and condensed phases have been simultaneously monitored using residual gas mass spectrometry and FTIR absorption spectroscopy, respectively. Barrierless nucleation of the metastable phases of both α-NAT (nitric acid trihydrate) and NAD (nitric acid dihydrate) has been observed when HNO3 was admitted to the SFR in the presence of a macroscopic thin film of pure H2O ice of typically 1 µm thickness. The stable β-NAT phase was spontaneously formed from the precursor α-NAT phase through irreversible thermal rearrangement beginning at 185 K. This facile growth scheme of nitric acid hydrates requires the presence of H2O ice at thicknesses in excess of approximately hundred nanometers. Absolute absorption cross sections in the mid-IR spectral range (700-4000 cm-1) of all three title compounds have been obtained after spectral subtraction of excess pure ice at temperatures characteristic of the upper troposphere/lower stratosphere. Prominent IR absorption frequencies correspond to the antisymmetric nitrate stretch vibration (ν3(NO3-)) in the range 1300 to 1420 cm-1 and the bands of hydrated protons in the range 1670 to 1850 cm-1 in addition to the antisymmetric O-H stretch vibration of bound H2O in the range 3380 to 3430 cm-1 for NAT.

  8. The Relative Roles of RONO2 and HNO3 as Sinks of NOX in the Denver Metropolitan Region and Colorado's Front Range

    NASA Astrophysics Data System (ADS)

    Sparks, T.; Ebben, C. J.; Wooldridge, P. J.; Cohen, R. C.

    2015-12-01

    Measurements of HNO3, total RONO2, NOX, and other relevant species, acquired during the DISCOVER-AQ and FRAPPE field campaigns in the Northern Front Range of Colorado during July-August 2014, are used to assess our understanding of the relative roles of RONO2 and HNO3 formation as sinks of NOX. Although HNO3 production was dominant in the region, RONO2 production was often of order 1/3 of the NOX sink. As NOX emissions decrease, our results indicate RONO2­ chemistry will be increasingly important to descriptions of the chemistry in the region.

  9. Laboratory studies of the nitric acid trihydrate - Implications for the south polar stratosphere

    NASA Technical Reports Server (NTRS)

    Hanson, David; Mauersberger, Konrad

    1988-01-01

    Vapor pressures of HNO3 and H2O have been measured over the trihydrate crystal, formed by vapor deposit on a glass surface. In the temperature range 190 to 205 K the two phase-equilibrium trihydrate/vapor was studied by adding and removing H2O. Coexistence equilibria vapor pressures of trihydrate/solid solutions of HNO3 in ice and of mono-/trihydrate were also measured. Results show that for typical mixing ratios of H2O and HNO3 found in the lower stratosphere (3 ppm H2O, 5 ppb HNO3) the trihydrate would start to form at temperatures about 7 K higher than the ice point. The pressure of atmospheric HNO3 would rapidly decrease as the atmosphere cools without large changes in partial pressures of H2O. These laboratory results provide information on the formation of polar stratospheric clouds containing H2O and HNO3.

  10. Quantum yields for OH production from 193 and 248 nm photolysis of HNO3 and H2O2

    NASA Astrophysics Data System (ADS)

    Schiffman, A.; Nelson, D. D., Jr.; Nesbitt, D. J.

    1993-05-01

    Flash kinetic spectroscopy in a flow tube is used to measure at room temperature the absolute yields for OH production from 193 and 248 nm photolysis of HNO3 and H2O2. The OH radicals are produced by excimer laser photolysis and probed via direct absorption of high resolution tunable IR laser light. The results indicate quantum yields for both precursors at both wavelengths which are less than the maximum possible values of 1 for H2O2. The present measurements are discussed in light of contrasting results suggested from other work.

  11. Heterogeneous conversion of N2O5 to HNO3 on background stratospheric aerosols - Comparisons of model results with data

    NASA Astrophysics Data System (ADS)

    Considine, David B.; Douglass, Anne R.; Stolarski, Richard S.

    1992-02-01

    The effects of heterogeneous processing by a parameterized lower stratospheric sulfate aerosol layer on model calculations were examined using a 2D photochemical model. Model results were compared with zonally averaged LIMS data on HNO3 and NO2 and in situ measurements of NO, NO(y), and ClO, taken by the ER-2 aircraft. The results obtained are contradictory: some comparisons favor heterogeneous chemistry, and some do not. It is suggested that the assumptions made to parameterize the sulfate aerosol chemistry result in a rate of heterogeneous processing that is too vigorous.

  12. Molecular weight of aquatic fulvic acids by vapor pressure osmometry

    USGS Publications Warehouse

    Aiken, G.R.; Malcolm, R.L.

    1987-01-01

    The molecular weights of aquatic fulvic acids extracted from five rivers were determined by vapor pressure osmometry with water and tetrahydrofuran as solvents. The values obtained ranged from 500 to 950 dallons, indicating that the molecular weights of aquatic fulvic acids are not as great as has been suggested in some other molecular weight studies. The samples were shown to be relatively monodisperse from radii of gyration measurements determined by small angle x-ray scattering. THF affords greater precision and accuracy than H2O in VPO measurements, and was found to be a suitable solvent for the determination of molecular weight of aquatic fulvic acid because it obviates the dissociation problem. An inverse correlation was observed with these samples between the concentration of Ca++ and Mg++ in the river water and the radii of gyration and molecular weights of the corresponding fulvic acid samples. ?? 1987.

  13. Commercial Alloys for Sulfuric Acid Vaporization in Thermochemical Hydrogen Cycles

    SciTech Connect

    Thomas M. Lillo; Karen M. Delezene-Briggs

    2005-10-01

    Most thermochemical cycles being considered for producing hydrogen include a processing stream in which dilute sulfuric acid is concentrated, vaporized and then decomposed over a catalyst. The sulfuric acid vaporizer is exposed to highly aggressive conditions. Liquid sulfuric acid will be present at a concentration of >96 wt% (>90 mol %) H2SO4 and temperatures exceeding 400oC [Brown, et. al, 2003]. The system will also be pressurized, 0.7-3.5 MPa, to keep the sulfuric acid in the liquid state at this temperature and acid concentration. These conditions far exceed those found in the commercial sulfuric acid generation, regeneration and handling industries. Exotic materials, e.g. ceramics, precious metals, clad materials, etc., have been proposed for this application [Wong, et. al., 2005]. However, development time, costs, reliability, safety concerns and/or certification issues plague such solutions and should be considered as relatively long-term, optimum solutions. A more cost-effective (and relatively near-term) solution would be to use commercially-available metallic alloys to demonstrate the cycle and study process variables. However, the corrosion behavior of commercial alloys in sulfuric acid is rarely characterized above the natural boiling point of concentrated sulfuric acid (~250oC at 1 atm). Therefore a screening study was undertaken to evaluate the suitability of various commercial alloys for concentration and vaporization of high-temperature sulfuric acid. Initially alloys were subjected to static corrosion tests in concentrated sulfuric acid (~95-97% H2SO4) at temperatures and exposure times up to 200oC and 480 hours, respectively. Alloys with a corrosion rate of less than 5 mm/year were then subjected to static corrosion tests at a pressure of 1.4 MPa and temperatures up to 375oC. Exposure times were shorter due to safety concerns and ranged from as short as 5 hours up to 144 hours. The materials evaluated included nickel-, iron- and cobalt

  14. Acid Vapor Weathering of Apatite and Implications for Mars

    NASA Technical Reports Server (NTRS)

    Hausrath, E. M.; Golden, D. C.; Morris, R. V.; Ming, D. W.

    2008-01-01

    Phosphorus is an essential nutrient for terrestrial life, and therefore may be important in characterizing habitability on Mars. In addition, phosphate mobility on Mars has been postulated as an indicator of early aqueous activity [1]. Rock surfaces analyzed by the Spirit Mars Exploration Rover indicate elemental concentrations consistent with the loss of a phosphate-containing mineral [2], and the highly altered Paso Robles deposit contains 5% P2O5, modeled as 8-10 % phosphate [3]. Depending on the pH of the solution, phosphate can exist as one of four charge states, which can affect its solubility, reactivity and mobility. Phosphate may therefore prove a useful and interesting tracer of alteration conditions on Mars. Acid vapor weathering has been previously studied as a potentially important process on Mars [4-6], and Paso Robles may have been formed by reaction of volcanic vapors with phosphate-bearing rock [3, 7]. Here we present preliminary results of acid vapor reactions in a Parr vessel [6] using fluorapatite, olivine and glass as single phases and in a mixture.

  15. Aerosol chamber study of optical constants and N2O5 uptake on supercooled H2SO4/H2O/HNO3 solution droplets at polar stratospheric cloud temperatures.

    PubMed

    Wagner, Robert; Naumann, Karl-Heinz; Mangold, Alexander; Möhler, Ottmar; Saathoff, Harald; Schurath, Ulrich

    2005-09-15

    The mechanism of the formation of supercooled ternary H(2)SO(4)/H(2)O/HNO(3) solution (STS) droplets in the polar winter stratosphere, i.e., the uptake of nitric acid and water onto background sulfate aerosols at T < 195 K, was successfully mimicked during a simulation experiment at the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. Supercooled sulfuric acid droplets, acting as background aerosol, were added to the cooled AIDA vessel at T = 193.6 K, followed by the addition of ozone and nitrogen dioxide. N(2)O(5), the product of the gas phase reaction between O(3) and NO(2), was then hydrolyzed in the liquid phase with an uptake coefficient gamma(N(2)O(5)). From this experiment, a series of FTIR extinction spectra of STS droplets was obtained, covering a broad range of different STS compositions. This infrared spectra sequence was used for a quantitative test of the accuracy of published infrared optical constants for STS aerosols, needed, for example, as input in remote sensing applications. The present findings indicate that the implementation of a mixing rule approach, i.e., calculating the refractive indices of ternary H(2)SO(4)/H(2)O/HNO(3) solution droplets based on accurate reference data sets for the two binary H(2)SO(4)/H(2)O and HNO(3)/H(2)O systems, is justified. Additional model calculations revealed that the uptake coefficient gamma(N(2)O(5)) on STS aerosols strongly decreases with increasing nitrate concentration in the particles, demonstrating that this so-called nitrate effect, already well-established from uptake experiments conducted at room temperature, is also dominant at stratospheric temperatures.

  16. Complexes of HNO3 and NO3 - with NO2 and N2O4, and their potential role in atmospheric HONO formation.

    PubMed

    Kamboures, Michael A; Raff, Jonathan D; Miller, Yifat; Phillips, Leon F; Finlayson-Pitts, Barbara J; Gerber, R Benny

    2008-10-21

    Calculations were performed to determine the structures, energetics, and spectroscopy of the atmospherically relevant complexes (HNO(3)).(NO(2)), (HNO(3)).(N(2)O(4)), (NO(3)(-)).(NO(2)), and (NO(3)(-)).(N(2)O(4)). The binding energies indicate that three of the four complexes are quite stable, with the most stable (NO(3)(-)).(N(2)O(4)) possessing binding energy of almost -14 kcal mol(-1). Vibrational frequencies were calculated for use in detecting the complexes by infrared and Raman spectroscopy. An ATR-FTIR experiment showed features at 1632 and 1602 cm(-1) that are attributed to NO(2) complexed to NO(3)(-) and HNO(3), respectively. The electronic states of (HNO(3)).(N(2)O(4)) and (NO(3)(-)).(N(2)O(4)) were investigated using an excited state method and it was determined that both complexes possess one low-lying excited state that is accessible through absorption of visible radiation. Evidence for the existence of (NO(3)(-)).(N(2)O(4)) was obtained from UV/vis absorption spectra of N(2)O(4) in concentrated HNO(3), which show a band at 320 nm that is blue shifted by 20 nm relative to what is observed for N(2)O(4) dissolved in organic solvents. Finally, hydrogen transfer reactions within the (HNO(3)).(NO(2)) and (HNO(3)).(N(2)O(4)) complexes leading to the formation of HONO, were investigated. In both systems the calculated potential profiles rule out a thermal mechanism, but indicate the reaction could take place following the absorption of visible radiation. We propose that these complexes are potentially important in the thermal and photochemical production of HONO observed in previous laboratory and field studies.

  17. Interaction of Ethyl Alcohol Vapor with Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Leu, Ming-Taun

    2006-01-01

    We investigated the uptake of ethyl alcohol (ethanol) vapor by sulfuric acid solutions over the range approx.40 to approx.80 wt % H2SO4 and temperatures of 193-273 K. Laboratory studies used a fast flow-tube reactor coupled to an electron-impact ionization mass spectrometer for detection of ethanol and reaction products. The uptake coefficients ((gamma)) were measured and found to vary from 0.019 to 0.072, depending upon the acid composition and temperature. At concentrations greater than approx.70 wt % and in dilute solutions colder than 220 K, the values approached approx.0.07. We also determined the effective solubility constant of ethanol in approx.40 wt % H2SO4 in the temperature range 203-223 K. The potential implications to the budget of ethanol in the global troposphere are briefly discussed.

  18. Evidence That Nitric Acid Increases Relative Humidity in Low-Temperature Cirrus Clouds

    NASA Technical Reports Server (NTRS)

    Gao, R. S.; Popp, P. J.; Fahey, D. W.; Marcy, T. P.; Herman, R. L.; Weinstock, E. M.; Baumgardner, D. G.; Garrett, T. J.; Rosenlof, K. H.; Thompson, T. L.

    2004-01-01

    In situ measurements of the relative humidity with respect to ice (RH(sub(i)) and of nitric acid (HNO3) were made in both natural and contrail cirrus clouds in the upper troposphere. At temperatures lower than 202 kelvin, RH(sub i) values show a sharp increase to average values of over 130% in both cloud types. These enhanced RH(sub i) values are attributed to the presence of a new class of NHO3- containing ice particles (Delta-ice). We propose that surface HNO3 molecules prevent the ice/vapor system from reaching equilibrium by a mechanism similar to that of freezing point depression by antifreeze proteins. Delta-ice represents a new link between global climate and natural and anthropogenic nitrogen oxide emissions. Including Delta-ice in climate models will alter simulated cirrus properties and the distribution of upper tropospheric water vapor.

  19. Kinetics of electron attachment to OH and HNO3 and mutual neutralization of Ar+ with NO2- and NO3- at 300 and 500 K

    NASA Astrophysics Data System (ADS)

    Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, A. A.

    2012-03-01

    The electron attachment rate constant to nitric acid (HNO3) has been measured in a flowing afterglow-Langmuir probe (FALP) apparatus at 300 and 500 K using three independent methods: the traditional FALP technique of monitoring electron depletion, "one-gas" VENDAMS (variable electron and neutral density attachment mass spectrometry), and "two-gas" VENDAMS. The three measurements are in agreement with a 300 K weighted average of 1.4 ± 0.3 × 10-7 cm3 s-1, 2 to 10 times higher than previously reported values. Attachment is primarily dissociative yielding NO2- as previously reported, but for the first time a small endothermic channel to produce OH- was also observed at 500 K. From the one-gas VENDAMS data, associative attachment to the OH produced in the primary attachment was found to occur with an effective two body rate constant of 1.2 ± _{0.7}^3 × 10-11 cm3 s-1 at 300 K, the first reported rate constant for this radical species. Finally, ion-ion neutralization rate constants of NO2- and NO3- with Ar+ were determined to be 5.2 ± _{2.5}^{1.5} × 10-8 and 4.5 ± 2.5 × 10-8 cm3 s-1 at 300 K, respectively.

  20. Kinetics of electron attachment to OH and HNO3 and mutual neutralization of Ar+ with NO2(-) and NO3(-) at 300 and 500 K.

    PubMed

    Shuman, Nicholas S; Miller, Thomas M; Viggiano, A A

    2012-03-28

    The electron attachment rate constant to nitric acid (HNO(3)) has been measured in a flowing afterglow-Langmuir probe (FALP) apparatus at 300 and 500 K using three independent methods: the traditional FALP technique of monitoring electron depletion, "one-gas" VENDAMS (variable electron and neutral density attachment mass spectrometry), and "two-gas" VENDAMS. The three measurements are in agreement with a 300 K weighted average of 1.4 ± 0.3 × 10(-7) cm(3) s(-1), 2 to 10 times higher than previously reported values. Attachment is primarily dissociative yielding NO(2)(-) as previously reported, but for the first time a small endothermic channel to produce OH(-) was also observed at 500 K. From the one-gas VENDAMS data, associative attachment to the OH produced in the primary attachment was found to occur with an effective two body rate constant of 1.2±(0.7) (3)×10(-11) cm(3) s(-1) at 300 K, the first reported rate constant for this radical species. Finally, ion-ion neutralization rate constants of NO(2)(-) and NO(3)(-) with Ar(+) were determined to be 5.2±(2.5) (1.5) × 10(-8) and 4.5 ± 2.5 × 10(-8) cm(3) s(-1) at 300 K, respectively.

  1. BrCl production in NaBr/NaCl/HNO3/O3 solutions representative of sea-salt aerosols in the marine boundary layer

    NASA Astrophysics Data System (ADS)

    Disselkamp, R. S.; Chapman, E. G.; Barchet, W. R.; Colson, S. D.; Howd, C. D.

    Atomic bromine and chlorine liberated from sea-salt aerosol is thought to play an important role in chemistry of the marine boundary layer. Despite numerous modeling studies, no prior experimental investigations of the oxidation of halide species contained in simulated, or actual, sea-salt solutions have been performed. We present laboratory data that examines chemistry in NaBr/NaCl/HNO3/O3 solutions at 290 K. Ozonation experiments were performed by flowing ozone in air through a nitric acid/salt solution and monitoring pH with time using an ion-sensitive electrode. The rate of oxidation was observed to be first order in ozone concentration and to have a non-first order bromide concentration dependence. Ion Chromatography was used to measure both bromide disappearance as well as oxidation products formed during the course of the reactions studied. Our measurements of the oxidation rate versus ion concentration indicate that the high ionic strength present in sea-salt aerosol will possess unique kinetics different from dilute solution behavior. In addition, our results are consistent with the reaction sequence O3 + H+ + Br- → O2 + HOBr and HOBr + Cl- + H+ → BrCl + H2O. These observations support the HOBr mediated Cl- oxidation process proposed previously (Vogt et al., 1996).

  2. A theoretical investigation of gaseous absorption by water droplets from SO2-HNO3-NH3-CO2-HCl mixtures

    NASA Technical Reports Server (NTRS)

    Adewuyi, Y. G.; Carmichael, G. R.

    1982-01-01

    A physical-chemical model is developed and used to investigate gaseous absorption by water droplets from trace gas mixtures. The model is an extension of that of Carmichael and Peters (1979) and includes the simultaneous absorption of SO2, NH3, HNO3, CO2, and HCl. Gas phase depletion is also considered. Presented results demonstrate that the absorption behavior of raindrops is strongly dependent on drop size, fall distance, trace gas concentrations, and the chemical and physical properties of the constituents of the mixture. In addition, when gas phase depletion is considered, the absorption rates and equilibrium values are also dependent on the precipitation rate itself. Also, the trace constituents liquid phase concentrations may be a factor of six or more lower when gas depletion is considered then when the depletion is ignored. However, the hydrogen ion concentration may be insensitive to the gas phase depletion.

  3. Kinetics of the Reactions of F((sup 2)P) and Cl((sup 2)P) with HNO3

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Wells, J. R.; Nicovich, J. M.

    1997-01-01

    The kinetics of the reactions of HNO3 with fluorine (k(sub 1)) and Chlorine (k(sub 2)) atoms have been studied by using a time-resolved long-path laser absorption technique to monitor the appearance of product NO3 radicals following 351-nm pulsed laser photolysis of X2/HNO3/He mixtures (X = F,Cl). Absolute rate coefficients for the F((sup 2)P) + HNO reaction have been determined over the temperature range 260-373 K. Between 260 and 320 K, the data are adequately represented by the Arrhenius expression k(sub 1)(T) = (6.0 +/- 2.6) x 10(exp -12) exp[(40 +/- 120)/T]cu cm/(molecule.s). Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10(exp -11)cu cm/(molecule.s) independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO3 production was observed in the experiments with X equals Cl, thus establishing that k(sub 2)(298 K) is less than 2 x 10(exp -16) cu cm/(molecule.s). The Cl((sup 2)P) + HNO reaction was also investigated by using a pulsed laser photolysis-resonance fluorescence technique to monitor the decay of Cl((sup 2)P). Upper limit values for k(sub 2) obtained from these experiments, in units of 10(exp -16)cu cm/(molecule.s), are 13 at 298 K and 10 at 400 K.

  4. Balloon profiles of stratospheric NO2 and HNO3 for testing the heterogeneous hydrolysis of N2O5 on sulfate aerosols

    NASA Technical Reports Server (NTRS)

    Webster, C. R.; May, R. D.; Allen, M.; Jaegle, L.; Mccormick, M. P.

    1994-01-01

    Simultaneous in situ measurements of stratospheric NO2, HNO3, HCl, and CH4 from 34 to 24 km were made in August 1992 from Palestine, Texas, using the Balloon-borne Laser In-Situ Sensor (BLISS) tunable diode laser spectrometer. Although the measurements of NO2, HNO3, and NO2/HNO3 agree well with gas-phase model calculations near 34 km where Stratospheric Aerosol and Gas Experiment (SAGE) 2 data show little sulfate aerosol, this is not true at the lower altitudes where SAGE 2 shows high aerosol loadings. At 24 km the BLISS NO2 and HNO3 measurements are 70% lower and 50% higher, respectively, than the gas phase model predictions, with a measured NO2/HNO3 ratio 5 times smaller. When the heterogeneous hydrolysis of N2O5 and ClONO2 on sulfate aerosol of surface area densities matching the SAGE 2 measurements is added to the model, good agreement with the BLISS measurements is found over the whole altitude range.

  5. Measurements of NO2, SO2, NH3, HNO3 and O3 in West African urban environments

    NASA Astrophysics Data System (ADS)

    Adon, Marcellin; Yoboué, Véronique; Galy-Lacaux, Corinne; Liousse, Catherine; Diop, Babakar; Doumbia, El Hadji Thierno; Gardrat, Eric; Ndiaye, Seydi Ababacar; Jarnot, Christian

    2016-06-01

    In this paper, we present the measurements of atmospheric gas concentrations of NO2, SO2, NH3, HNO3, and O3 performed at two traffic sites in the context of the POLCA (Pollution of African Capitals) program. These gases were measured using a passive sampling technique from Jan. 2008 to Dec. 2009 at Dakar and from Jun. 2008 to Dec. 2009 at Bamako. In addition, during these periods there were two intensive measurement campaigns (from 19 Jan. to 2 Feb. 2009 at Bamako and from 30 Nov. to 13 Dec. 2009 at Dakar) where real-time active analysers were used to measure NO2 and SO2. Results show that Dakar has a pollution level for NO2 and SO2 higher than that of Bamako, whereas it is lower for NH3 concentrations. Monthly values of NO2 range between 21.1 and 43.5 ppb in Dakar with an annual mean concentration of 31.7 ppb (59.6 μg/m3). NO2 values in Bamako are 9.4-22.6 ppb with a mean of 16.2 ppb. At Dakar, the mean annual NO2 limit value (21.3 ppb or 40 μg/m3) recommended by the World Health Organization (WHO) is widely exceeded. The mean annual concentration of SO2 is 15.9 ppb in Dakar and 3.6 ppb in Bamako. These differences may be explained by different sources of traffic between Bamako (with mainly gasoline vehicles) and Dakar (with mainly diesel vehicles). The annual mean NH3 concentration is about two times higher in Bamako (46.7 ppb) than in Dakar (21.1 ppb). In addition to other possible sources, we assume that the ammonia from domestic fires and uncontrolled garbage incineration may have more influence at Bamako than at Dakar. The mean annual concentrations of HNO3 and O3 are 1.3 ppb and 7.7 ppb in Dakar and 0.6 ppb and 5.1 ppb in Bamako, respectively. Seasonal variation in measured gas concentrations are low in Bamako and more pronounced in Dakar, except for HNO3 and NH3. At Dakar, NO2 and SO2 daily mean concentrations are higher during the weekdays than on weekends, when urban activities are reduced, whereas at Bamako, no significant difference was observed

  6. Observations and Modeling of Composition of Upper Troposphere/Lower Stratosphere (UTILS): Isentropic Mixing Events and Morphology of HNO3 as Observed by HIRDLS and Comparison with Results from Global Modeling Initiative

    NASA Technical Reports Server (NTRS)

    Rodriquez, J. M.; Douglass, A.R.; Yoshida, Y.; Strahan, S.; Duncan, B.; Olsen, M.; Gille, J.; Yudin, V.; Nardi, B.

    2008-01-01

    isentropic exchange of air masses between the tropical upper troposphere and mid-latitude lowermost stratosphere (the so-called "middle world") is an important pathway for stratospheric-tropospheric exchange. A seasonal, global view of this process has been difficult to obtain, in part due to the lack of the vertical resolution in satellite observations needed to capture the laminar character of these events. Ozone observations at a resolution of about 1 km from the High Resolution Dynamic Limb Sounder (HIRDLS) on NASA's Aura satellite show instances of these intrusions. Such intrusions should also be observable in HN03 observations; however, the abundances of nitric acid could be additionally controlled by chemical processes or incorporation and removal into ice clouds. We present a systematic examination of the HIRDLS data on O3 and HNO3 to determine the seasonal and spatial characteristics of the distribution of isentropic intrusions. At the same time, we compare the observed distributions with those calculated by the Global Modeling Initiative combined tropospheric-stratospheric model, which has a vertical resolution of about I km. This Chemical Transport Model (CTM) is driven by meteorological fields obtained from the GEOS-4 system of NASA/Goddard Global Modeling and Assimilation Office (GMAO), for the Aura time period, at a vertical resolution of about 1 km. Such comparison brings out the successes and limitations of the model in representing isentropic stratospheric-tropospheric exchange, and the different processes controlling HNO3 in the UTAS.

  7. Single-step microwave digestion with HNO(3) alone for determination of trace elements in coal by ICP spectrometry.

    PubMed

    Wang, Jie; Nakazato, Tetsuya; Sakanishi, Kinya; Yamada, Osamu; Tao, Hiroaki; Saito, Ikuo

    2006-02-28

    A microwave digestion method with HNO(3) alone was conducted at a temperature as high as 250 degrees C for determination of 19 trace elements (Li, Be, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Cd, Cs, Ba, Hg, and Pb) in coal jointly by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and flow injection ICP-MS (FI-ICP-MS). The validity of determination was assessed by using three standard coals, SRM 1632c, BCR 180, and SARM 19. It was found that the high-temperature digestion led to an extensive decomposition of the organic matrix and clay in coal, and no dissolved and solid carbon remained in the final solution after evaporation. Good recoveries were observed for all trace elements in three coals, with the exception of V, Rb, and Cs in high-ash SARM 19. Additionally, FI-ICP-MS combined with the present digestion without evaporation pretreatment was proved to be a rapid and efficient approach for determination of ultra-trace elements such as Se, Cd, and Hg in coal.

  8. Uptake of HNO3 to deliquescent sea-salt particles: a study using the short-lived radioactive isotope tracer 13N

    NASA Astrophysics Data System (ADS)

    Guimbaud, C.; Arens, F.; Gutzwiller, L.; Gäggeler, H. W.; Ammann, M.

    2002-10-01

    The uptake of HNO3 to deliquescent airborne sea-salt particles (RH = 55%, P = 760 torr, T = 300 K) at concentrations from 2 to 575 ppbv is measured in an aerosol flow tube using 13N as a tracer. Small particles ( 70 nm diameter) are used in order to minimize the effect of diffusion in the gas phase on the mass transfer. Below 100 ppbv, an uptake coefficient (gupt) of 0.50 ± 0.20 is derived. At higher concentrations, the uptake coefficient decreases along with the consumption of aerosol chloride. Data interpretation is further supported by using the North American Aerosol Inorganics Model (AIM), which predicts the aqueous phase activities of ions and the gas-phase partial pressures of H2O, HNO3, and HCl at equilibrium for the NaCl/HNO3/H2O system. These simulations show that the low concentration data are obtained far from equilibrium, which implies that the uptake coefficient derived is equal to the mass accommodation coefficient under these conditions. The observed uptake coefficient can serve as input to modeling studies of atmospheric sea-salt aerosol chemistry. The main sea-salt aerosol burden in the marine atmosphere is represented by coarse mode particles (> 1 µm diameter). This implies that diffusion in the gas-phase is the limiting step to HNO3 uptake until the sea-salt has been completely processed.

  9. Stratospheric HNO3 measurements from 0.002/cm resolution solar occultation spectra and improved spectroscopic line parameters in the 5.8-micron region

    NASA Astrophysics Data System (ADS)

    Goldman, A.; Murcray, F. J.; Blatherwick, R. D.; Kosters, J. J.; Murcray, D. G.; Rinsland, C. P.; Flaud, J.-M.; Camy-Peyret, C.

    1992-02-01

    Very-high-resolution FWHM solar-occultation spectra are investigated with a balloon-borne interferometer using revised spectroscopic line parameters for HNO3, O3, and H2O. The O3 and H2O data are evaluated to determine their capacity for interference in the HNO3 line which is studied in the nu sub 2 band at 5.8 microns. The line parameters developed with the stratospheric data are compared to data based on a HITRAN compilation as well as laboratory spectra with a 0.002/cm resolution. The line list is calculated and shown to include J and Ka transitions which improve the line parameters for HNO3 by accounting for the weaker absorption features in the stratospheric spectra. The stratospheric HNO3 profile developed analytically is compared to those based on reported measurements, and the one developed with the stratospheric solar spectra is found to be consistent with the measurements and confirm inherent measurement biases.

  10. Intercomparison of Clean Air Status and Trends Network (CASTNET) NO3 - and HNO3 Measurements with Data from Other Monitoring Programs

    EPA Science Inventory

    The EPA Clean Air Status and Trends Network (CASTNET) utilizes an open face filter pack system to measure concentrations of atmospheric sulfur and nitrogen species. The purpose of this study was to estimate the uncertainty in seasonal and annual concentrations of HNO3, NO3 - , ...

  11. Stratospheric HNO3 measurements from 0.002/cm resolution solar occultation spectra and improved spectroscopic line parameters in the 5.8-micron region

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Blatherwick, R. D.; Kosters, J. J.; Murcray, D. G.; Rinsland, C. P.; Flaud, J.-M.; Camy-Peyret, C.

    1992-01-01

    Very-high-resolution FWHM solar-occultation spectra are investigated with a balloon-borne interferometer using revised spectroscopic line parameters for HNO3, O3, and H2O. The O3 and H2O data are evaluated to determine their capacity for interference in the HNO3 line which is studied in the nu sub 2 band at 5.8 microns. The line parameters developed with the stratospheric data are compared to data based on a HITRAN compilation as well as laboratory spectra with a 0.002/cm resolution. The line list is calculated and shown to include J and Ka transitions which improve the line parameters for HNO3 by accounting for the weaker absorption features in the stratospheric spectra. The stratospheric HNO3 profile developed analytically is compared to those based on reported measurements, and the one developed with the stratospheric solar spectra is found to be consistent with the measurements and confirm inherent measurement biases.

  12. Measurements of HNO3 and N2O5 using Ion drift - Chemical Ionization Mass Spectrometry during the MCMA - 2006 Campaign

    NASA Astrophysics Data System (ADS)

    Zheng, J.; Zhang, R.; Fortner, E. C.; Molina, L.; Aiken, A. C.; Jimenez, J. L.; Gäggeler, K.; Dommen, J.; Dusanter, S.; Stevens, P. S.; Tie, X.

    2008-03-01

    An ion drift - chemical ionization mass spectrometry (ID-CIMS) was deployed in Mexico City between 5 and 31 March to measure HNO3 and N2O5 during the 2006 Mexico City Metropolitan Area (MCMA) field campaign. The observation site, T0, was located at the Instituto Mexicano del Petróleo at the center of the Mexico City Basin with major emissions of pollutants from both domestic and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and in the early morning, increased steadily from around 09:00 a.m. central standard time (CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early afternoon, and declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS) showed a good correlation in the HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with aerosol nitrate, suggesting that the gaseous HNO3 concentration was controlled by the gas-particle partitioning process. During most times of the MCMA 2006 field campaign, N2O5 was found to be under the detection limit (about 20 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio (>100 ppb) during the night. With one exception on 26 March 2006, about 40 ppt N2O5 was observed during the late afternoon and early evening hours under a cloudy condition, before NO built up at the surface site. The results revealed that during the 2006 MCMA field campaign HNO3 was primarily produced by the reaction of OH with NO2 and regulated by gas/particle partitioning, and HNO3 production from N2O5 hydrolysis during the nighttime was small because of high NO and low O3 concentrations near the surface.

  13. Corrosion of Type 7075-T73 Aluminum in a 10% HNO3 + Fe2(SO4)3 Deoxidizer Solution

    NASA Astrophysics Data System (ADS)

    Savas, Terence P.; Earthman, James C.

    2009-03-01

    Localized corrosion damage in Type 7075-T73 aluminum was investigated for a HNO3 + Fe2(SO4)3 deoxidizer solution which is frequently used for surface pretreatment prior to anodizing. The corrosion damage was quantified in the time domain using the electrochemical noise resistance ( Rn) and in the frequency domain using the spectral noise impedance ( Rsn). The Rsn was derived from an equivalent electrical circuit model that represented the corrosion cell implemented in the present study. These data are correlated to scanning electron microscopy (SEM) examinations and corresponding statistical analysis based on digital image analysis of the corroded surfaces. Other data used to better understand the corrosion mechanisms include the open circuit potential (OCP) and coupling-current time records. Based on statistical analysis of the pit structures for 600 and 1200 s exposures, the best fit was achieved with a 3-paramater lognormal distribution. It was observed for the 1200 s exposure that a small population of pits continued to grow beyond a threshold critical size of 10 μm. In addition, significant grain boundary attack was observed after 1200 s exposure. These data are in good agreement with the electrochemical data. Specifically, the Rn was computed to be 295 and 96 Ω-cm2 for 600 and 1200 s exposures, respectively. The calculated value of Rsn, theoretically shown to be equal to Rn in the low frequency limit, was higher than Rn for a 1200 s exposure period. However, better agreement between the Rn and Rsn was found for frequencies above 0.01 Hz. Experimental results on the measurement performance for potassium chloride (KCl) saturated double-junction Ag/AgCl and single-junction Hg/Hg2Cl2 reference electrodes in the low-pH deoxidizer solution are also compared.

  14. Identification of the HNO3 3 nu(sub 9) - nu(sub 9) band Q branch in stratospheric solar occultation spectra

    NASA Technical Reports Server (NTRS)

    Perrin, A.; Flaud, J.-M.; Camy-Peyret, C.; Goldman, A.; Rinsland, C. P.; Gunson, M. R.

    1994-01-01

    The spectroscopic identification for the HNO3 3 nu(sub 9) - nu(sub 9) band Q branch at 830.4/cm is reported based on 0.01/cm resolution solar occultation spectra of the lower stratosphere recorded by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer and a recent analysis of this band. Least-squares fits to 0.0025/cm resolution laboratory spectra in the Q branch region indicate an integrated intensity of 0.529 x 10(exp -18)/cm/mol/sq cm at 296 K for this weak band. Stratospheric HNO3 retrievals derived from the ATMOS data are consistent with this value within its estimated uncertainty of about +/- 30%. A set of spectroscopic line parameters suitable for atmospheric studies has been generated.

  15. Comparison of correlative data with HNO3 version 7 from the CLAES instrument deployed on the NASA Upper Atmosphere Research Satellite

    NASA Astrophysics Data System (ADS)

    Kumer, J. B.; Mergenthaler, J. L.; Roche, A. E.; Nightingale, R. W.; Ely, G. A.; Uplinger, W. G.; Gille, J. C.; Massie, S. T.; Bailey, P. L.; Gunson, M. R.; Abrams, M. C.; Toon, G. C.; Sen, B.; Blavier, J.-F.; Stachnik, R. A.; Webster, C. R.; May, R. D.; Murcray, D. G.; Murcray, F. J.; Goldman, A.; Traub, W. A.; Jucks, K. W.; Johnson, D. G.

    1996-04-01

    The cryogenic limb array etalon spectrometer (CLAES) aboard UARS made near-global measurements of HNO3 and 388 days from January 9, 1992, to April 25, 1993, have been processed to data version 7 (V7). Results from UARS instruments, including CLAES, the improved stratospheric and mesospheric sounder, and the microwave limb sounder, provide the first near-global documentation of the evolution of denitrification in the Antarctic 1992 winter and spring vortex. We provide a description of the CLAES HNO3 V7 quality that includes comparisons with correlative measurements to assess overall quality, accuracy, and precision. Correlative profiles of volume mixing ratio (vmr) included those obtained by the space shuttle deployed ATMOS in two missions, March-April 1992 and April 1993, data from a variety of balloon-borne instruments at midlatitude (11 profiles), and in high-latitude northern winter (six profiles), and LIMS data. In general, the CLAES V7 HNO3 maximum values of vmr were of the order of 6-15% less than correlative for CLAES values ≤8 parts per billion by volume (ppbv). However, when CLAES peak vmr values were 10 to 13 ppbv, then CLAES values exceeded correlative by 0-7%. The comparisons were within the combined instrumental error estimates, or observed measurement variability, for the large majority of comparisons. As discussed, the retrieval of future versions will utilize updated spectral parameters and will also correct for a small uncompensated drift in radiometric calibration that occurred in the latter part of the mission. This is expected to improve the comparisons in the ≤8 ppbv range, perhaps at the expense of those in the ≥8 ppbv range. The data obtained January 9 to April 15, 1992, in comparison with data obtained January 9 to April 15, 1993, reveal strikingly evident 1-year period deseasonalized trends on a global basis. These trends agree quantitatively with available correlative data suitable for trend analysis. These include ATMOS in the

  16. Extraction of Pd(II), Rh(III) and Ru(III) from HNO(3) aqueous solution to betainium bis(trifluoromethanesulfonyl)imide ionic liquid.

    PubMed

    Sasaki, Kotoe; Takao, Koichiro; Suzuki, Tomoya; Mori, Takahiro; Arai, Tsuyoshi; Ikeda, Yasuhisa

    2014-04-21

    Extraction efficiencies of Pd(ii), Rh(iii), and Ru(iii) from HNO3(aq) to [Hbet][Tf2N] were demonstrated, i.e., Pd(ii) is the most extractable, Rh(iii) is medium extractable, and Ru(iii) is the least extractable. The extraction seems to proceed through coordination of betaine to the metal ions and the cation exchange of the formed complex with H(+).

  17. Complexation of mercury(II) with 1-Phenyl-2,3-dimethylpyrazoline-5-thione in 0.1 mol/L HNO3 at 273-338 K

    NASA Astrophysics Data System (ADS)

    Beknazarova, N. S.; Shoalifov, Dzh. O.; Amindzhanov, A. A.; Safarmamadov, S. M.

    2016-12-01

    The complexation of mercury(II) with 1-phenyl-2,3-dimethylpyrazoline-5-thione is studied by means of potentiometry in 0.1 mol/L HNO3 at 273-338 K. The composition of the complexes is determined and their stepwise stability constants are calculated. A pattern is found in altering the stepwise stability constants as the temperature and number of attached 1-phenyl-2,3-dimethylpyrazoline-5-thione molecules rise.

  18. The role of ion-molecule reactions in the conversion of N2O5 to HNO3 in the stratosphere

    NASA Astrophysics Data System (ADS)

    Bohringer, H.; Fahey, D. W.; Fehsenfeld, F. C.; Ferguson, E. E.

    1983-02-01

    The role of several ion-molecule reactions in the conversion of N2O5 to HNO3 was investigated. In the proposed conversion, an N2O5 molecule would react with an H2O molecule clustered to an inert ion to produce two HNO3 molecules. Subsequent clustering of an H2O molecule to the inert ion would make the reaction catalytic. If such an ion-catalyzed conversion of N2O5 to HNO3 occurs, it would probably play a role in the stratospheric chemistry at high latitudes in winter. Reaction rate constant measurements made in a flowing afterglow apparatus flor hydrated H3O(+), H(+)(CH3CN)m(m equals 1,2,3), and several negative ions reacting with N2O5 are presented. Slow rate constants were found for these ions for hydration levels that are predominant in the stratosphere. With the known stratospheric ion density, these slow rate constants preclude significant N2O5 conversion by ion-molecule reactions.

  19. Recent Advances in Detection of Ammonia and Nitric Acid on Short Timescales Suitable for Eddy Covariance Flux Measurements

    NASA Astrophysics Data System (ADS)

    Roscioli, Joseph; Herndon, Scott; Zahniser, Mark; Nelson, David; McManus, Barry

    2015-04-01

    Ammonia and nitric acid play important roles in aerosol, cloud, and NOx chemistry. Accurately measuring these species' concentrations on a fast timescale has historically been complicated due to their tendency to slowly and irreversibly interact with instrument surfaces. Here we present recent efforts aimed at mitigating these effects using new inlet technologies. First, an inlet that combines an inertial impactor with a pressure drop across a critical orifice provides particle removal without a traditional filter. This approach is used to reduce instrumental time responses for NH3 and HNO3 to 3-15 seconds. Second, a further reduction in time response is achieved by entraining functionalized perfluoroalkane vapor into the inlet sampling stream. This "active passivation" method is used to achieve time responses of ~0.5 seconds for both NH3 and HNO3, and is found to be applicable to a variety of inlet designs. These technologies enable fast time response sampling suitable for eddy covariance flux measurements.

  20. Time Series of Trace Gas Profiles of O3, N2o, Ch4, Hf, Hcl, and Hno3 As Retrieved From Ground Based Ftir Observations In Winter 2000/2001 and 2001/2002 At Kiruna (sweden)

    NASA Astrophysics Data System (ADS)

    Griesfeller, A.; Blumenstock, T.; Hase, F.; Höpfner, M.; Ruhnke, R.; Arvelius, J.; Raffalski, U.; Kondo, Y.

    Atmospheric absorption spectra using the sun as the source of radiation were recorded by ground based FTIR (Fourier Transform InfraRed) spectrometers at Kiruna (Swe- den, 68N, 20E) during winter and early spring since winter 1990. Since March 1996 a Bruker 120 HR is in operation at the IRF (Swedish Institute of Space Physics). It is operated permanently and it is part of the NDSC (Network for the Detection of Strato- spheric Change). The FTIR spectra have been analyzed with the radiative transfer code KOPRA (Karlsruhe Optimized and Precise Radiative transfer Algorithm) and the re- trieval code PROFFIT (Profile Fit) using Tikhonov-Phillips approach. Zenith column amounts (ZCA) of several trace gases like O3, N2O, CH4, HF, HCl, ClONO2, NO, NO2, and HNO3 have been derived from these spectra. In case of some important species as O3, N2O, CH4, HF, HCl, and HNO3 also reasonable information on the vertical concentration profiles can be derived. Since winter 1999/2000 data analysis is performed in near real time during the campaigns. These time series of ZCA and profiles will be presented for the winters of 2000/2001 and 2001/2002 and discussed in terms of chlorine activation and deactivation, ozone loss, and sequestration of ni- tric acid in PSCs in the polar vortex. Winter 2000/2001 is of interest due to a long lasting break-up of the polar vortex. Therefore a great variability in many gases is ob- served and will be discussed. In addition the results will be compared to results from KASIMA (Karlsruhe Simulation Model of the Middle Atmosphere).

  1. Adipic and malonic acid aqueous solutions: surface tensions and saturation vapor pressures.

    PubMed

    Riipinen, Ilona; Koponen, Ismo K; Frank, Göran P; Hyvärinen, Antti-Pekka; Vanhanen, Joonas; Lihavainen, Heikki; Lehtinen, Kari E J; Bilde, Merete; Kulmala, Markku

    2007-12-20

    The surface tension of adipic aqueous solutions was measured as a function of temperature (T=278-313 K) and adipic acid mole fraction (X=0.000-0.003) using the Wilhelmy plate method. A parametrization fitted to these data is presented. The evaporation rates of binary water-malonic and water-adipic acid droplets were measured with a TDMA technique at different temperatures (T=293-300 K) and relative humidities (58-80%), and the saturation vapor pressures of subcooled liquid malonic and adipic acids were derived from the data using a binary evaporation model. The temperature dependence of the vapor pressures was obtained as least-squares fits to the derived vapor pressures: ln(Psat,l) (Pa)=220.2389-22634.96/T (K)-26.66767 ln T (K) for malonic acid and ln(Psat,l) (Pa)=140.6704-18230.97/T (K)-15.48011 ln T (K) for adipic acid.

  2. What Is the Boiling Point and Heat of Vaporization of Sulfuric Acid?

    ERIC Educational Resources Information Center

    Myers, R. Thomas

    1983-01-01

    Discusses the values presented in various handbooks for the boiling point and heat of vaporization of sulfuric acid, noting discrepencies. Analyzes various approaches to data presentation, discussing the data on sulfuric acid in light of the Trouton constant. Points out the need for a more critical use of tables. (JM)

  3. Robust antifogging antireflective coatings on polymer substrates by hydrochloric acid vapor treatment.

    PubMed

    Li, Tong; He, Junhui; Yao, Lin; Geng, Zhi

    2015-04-15

    Antireflective coatings on polymer substrates have received significant attention for their potential applications. In this paper, robust microporous antifogging antireflective coatings on polymer substrates were prepared from acid-catalyzed silica sol followed by hydrochloric acid vapor solidification at mild temperature below glass transition temperatures of common polymers. The coatings passed 3H pencil hardness test, sand flow test and water-drop test. They had excellent antireflective and antifogging properties. The maximum transmittance of coatings on PMMA substrates reached 100.0% (the maximum transmittance wavelength could be regulated) and average transmittance reached 99.0% in 400-800 nm. The advantage and mechanism of hydrochloric acid vapor solidification and mechanical strength enhancement of coatings are discussed in contrast to ammonia vapor treatment and air vapor treatment. The hydrochloric acid vapor treatment results in a dense integrated microporous film structure. Optical properties were characterized by a UV-Vis spectrophotometer. Surface wettability was studied by a contact angle/interface system. Surface morphologies and structures of coatings were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atom force microscopy (AFM).

  4. Uptake of CO2, SO2, HNO3 and HCl on calcite (CaCO3) at 300 K: mechanism and the role of adsorbed water.

    PubMed

    Santschi, Ch; Rossi, M J

    2006-06-01

    All experimental observations of the uptake of the four title compounds on calcite are consistent with the presence of a reactive bifunctional surface intermediate Ca(OH)(HCO3) that has been proposed in the literature. The uptake of CO2 and SO2 occurs on specific adsorption sites of crystalline CaCO3(s) rather than by dissolution in adsorbed water, H2O(ads). SO2 primarily interacts with the bicarbonate moiety whereas CO2, HNO3 and HCl all react first with the hydroxyl group of the surface intermediate. Subsequently, the latter two react with the bicarbonate group to presumably form Ca(NO3)2 and CaCl2.2H2O. The effective equilibrium constant of the interaction of CO2 with calcite in the presence of H2O(ads) is kappa = deltaCO2/(H2O(ads)[CO2]) = 1.62 x 10(3) bar(-1), where CO2 is the quantity of CO2 adsorbed on CaCO3. The reaction mechanism involves a weakly bound precursor species that is reversibly adsorbed and undergoes rate-controlling concurrent reactions with both functionalities of the surface intermediate. The initial uptake coefficients gamma0 on calcite powder depend on the abundance of H2O(ads) under the present experimental conditions and are on the order of 10(-4) for CO2 and 0.1 for SO2, HNO3 and HCl, with gamma(ss) being significantly smaller than gamma0 for HNO3 and HCl, thus indicating partial saturation of the uptake. At 33% relative humidity and 300 K there are 3.5 layers of H2O adsorbed on calcite that reduce to a fraction of a monolayer of weakly and strongly bound water upon pumping and/or heating.

  5. LIMS Instrument Package (LIP) balloon experiment: Nimbus 7 satellite correlative temperature, ozone, water vapor, and nitric acid measurements

    NASA Technical Reports Server (NTRS)

    Lee, R. B., III; Gandrud, B. W.; Robbins, D. E.; Rossi, L. C.; Swann, N. R. W.

    1982-01-01

    The Limb Infrared Monitor of the Stratosphere (LIMS) LIP balloon experiment was used to obtain correlative temperature, ozone, water vapor, and nitric acid data at altitudes between 10 and 36 kilometers. The performance of the LIMS sensor flown on the Nimbus 7 Satellite was assessed. The LIP consists of the modified electrochemical concentration cell ozonesonde, the ultraviolet absorption photometric of ozone, the water vapor infrared radiometer sonde, the chemical absorption filter instrument for nitric acid vapor, and the infrared radiometer for nitric acid vapor. The limb instrument package (LIP), its correlative sensors, and the resulting data obtained from an engineering and four correlative flights are described.

  6. Comparing data obtained from ground-based measurements of the total contents of O3, HNO3,HCl, and NO2 and from their numerical simulation

    NASA Astrophysics Data System (ADS)

    Virolainen, Ya. A.; Timofeyev, Yu. M.; Polyakov, A. V.; Ionov, D. V.; Kirner, O.; Poberovskii, A. V.; Imhasin, H. Kh.

    2016-01-01

    Chemistry climate models of the gas composition of the atmosphere make it possible to simulate both space and time variations in atmospheric trace-gas components (TGCs) and predict their changes. Both verification and improvement of such models on the basis of a comparison with experimental data are of great importance. Data obtained from the 2009-2012 ground-based spectrometric measurements of the total contents (TCs) of a number of TGCs (ozone, HNO3, HCl, and NO2) in the atmosphere over the St. Petersburg region (Petergof station, St. Petersburg State University) have been compared to analogous EMAC model data. Both daily and monthly means of their TCs for this period have been analyzed in detail. The seasonal dependences of the TCs of the gases under study are shown to be adequately reproduced by the EMAC model. At the same time, a number of disagreements (including systematic ones) have been revealed between model and measurement data. Thus, for example, the EMAC model underestimates the TCs of NO2, HCl, and HNO3, when compared to measurement data, on average, by 14, 22, and 35%, respectively. However, the TC of ozone is overestimated by the EMAC model (on average, by 12%) when compared to measurement data. In order to reveal the reasons for such disagreements between simulated and measured data on the TCs of TGCs, it is necessary to continue studies on comparisons of the contents of TGCs in different atmospheric layers.

  7. Evaluation of sampling methods for measuring exposure to volatile inorganic acids in workplace air. Part 1: sampling hydrochloric acid (HCl) and nitric acid (HNO₃) from a test gas atmosphere.

    PubMed

    Howe, Alan; Musgrove, Darren; Breuer, Dietmar; Gusbeth, Krista; Moritz, Andreas; Demange, Martine; Oury, Véronique; Rousset, Davy; Dorotte, Michel

    2011-08-01

    Historically, workplace exposure to the volatile inorganic acids hydrochloric acid (HCl) and nitric acid (HNO(3)) has been determined mostly by collection on silica gel sorbent tubes and analysis of the corresponding anions by ion chromatography (IC). However, HCl and HNO(3) can be present in workplace air in the form of mist as well as vapor, so it is important to sample the inhalable fraction of airborne particles. As sorbent tubes exhibit a low sampling efficiency for inhalable particles, a more suitable method was required. This is the first of two articles on "Evaluation of Sampling Methods for Measuring Exposure to Volatile Inorganic Acids in Workplace Air" and describes collaborative sampling exercises carried out to evaluate an alternative method for sampling HCl and HNO(3) using sodium carbonate-impregnated filters. The second article describes sampling capacity and breakthrough tests. The method was found to perform well and a quartz fiber filter impregnated with 500 μL of 1 M Na(2)CO(3) (10% (m/v) Na(2)CO(3)) was found to have sufficient sampling capacity for use in workplace air measurement. A pre-filter is required to remove particulate chlorides and nitrates that when present would otherwise result in a positive interference. A GSP sampler fitted with a plastic cone, a closed face cassette, or a plastic IOM sampler were all found to be suitable for mounting the pre-filter and sampling filter(s), but care has to be taken with the IOM sampler to ensure that the sampler is tightly closed to avoid leaks. HCl and HNO(3) can react with co-sampled particulate matter on the pre-filter, e.g., zinc oxide, leading to low results, and stronger acids can react with particulate chlorides and nitrates removed by the pre-filter to liberate HCl and HNO(3), which are subsequently collected on the sampling filter, leading to high results. However, although there is this potential for both positive and negative interferences in the measurement, these are unavoidable

  8. Trajectory Studies of Large HNO3-Containing PSC Particles in the Arctic: Evidence for the Role of NAT

    NASA Technical Reports Server (NTRS)

    McKinney, K. A.; Wennberg, P. O.; Dhaniyala, S.; Fahey, D. W.; Northway, M. J.; Kuenzi, K. F.; Kleinboehl, A.; Sinnhuber, M.; Kuellmann, H.; Bremer, H.; Mahoney, M. J.; Bui, T. P.

    2004-01-01

    Large (5 to >20 micron diameter) nitric-acid-containing polar stratospheric cloud (PSC) particles were observed in the Arctic stratosphere during the winter of 1999-2000. We use a particle growth and sedimentation model to investigate the environment in which these particles grew and the likely phase of the largest particles. Particle trajectory calculations show that, while simulated nitric acid dihydrate (NAD) particle sizes are significantly smaller than the observed maximum particle sizes, nitric acid trihydrate (NAT) particle trajectories are consistent with the largest observed particle sizes.

  9. Topical and vapor toxicity of saturated fatty acids to the German cockroach (Dictyoptera: Blattellidae).

    PubMed

    Sims, Steven R; Balusu, Rammohan R; Ngumbi, Esther N; Appel, Arthur G

    2014-04-01

    Topical and fumigant toxicity of saturated aliphatic fatty acids with chain lengths of C1 through C14 were determined against the German cockroach, Blattella germanica (L.). In the C1 to C11 series, topical toxicity (LD50 in milligram per adult male) ranged from 0.145 (C1) to 0.322 mg (C2). Toxicity declined dramatically with C12 and C14 acids whose LD50 values could not be calculated. The relative fumigation toxicity (LC50 in microliter per liter) of C1 through C5 acids was positively correlated with topical toxicity with values ranging from 6.159 (C3) to 12.302 microl/liter (C2). Fumigant toxicity decreased sharply with C6 (LC50 = 37.691 microl/liter) and there was no mortality of cockroaches exposed to vapors from C7 to C14 acids. The low fumigant toxicity of the C6 to C11 acids was correlated with their relatively low vapor pressure, but differences in diffusion of the vapors into the spiracles and subsequent passage to the target sites may have also been involved.

  10. Improvement of microwave-assisted digestion of milk powder with diluted nitric acid using oxygen as auxiliary reagent

    NASA Astrophysics Data System (ADS)

    Bizzi, Cezar A.; Barin, Juliano S.; Garcia, Edivaldo E.; Nóbrega, Joaquim A.; Dressler, Valderi L.; Flores, Erico M. M.

    2011-05-01

    The feasibility of using diluted HNO 3 solutions under oxygen pressure for decomposition of whole and non-fat milk powders and whey powder samples has been evaluated. Digestion efficiency was evaluated by determining the carbon content in solution (digests) and the determination of Ca, Cd, Cu, Fe, K, Mg, Mn, Mo, Na, Pb and Zn was performed by inductively coupled plasma optical emission spectrometry and Hg by chemical vapor generation coupled to inductively coupled plasma mass spectrometry. Samples (up to 500 mg) were digested using HNO 3 solutions (1 to 14 mol L - 1 ) and the effect of oxygen pressure was evaluated between 2.5 and 20 bar. It was possible to perform the digestion of 500 mg of milk powder using 2 mol L - 1 HNO 3 with oxygen pressure ranging from 7.5 to 20 bar with resultant carbon content in digests lower than 1700 mg L - 1 . Using optimized conditions, less than 0.86 mL of concentrated nitric acid (14 mol L - 1 ) was enough to digest 500 mg of sample. The accuracy was evaluated by determination of metal concentrations in certified reference materials, which presented an agreement better than 95% (Student's t test, P < 0.05) for all the analytes.

  11. Measurements of HNO3, SO2 High Resolution Aerosol SO4 (sup 2-), and Selected Aerosol Species Aboard the NASA DC-8 Aircraft: During the Transport and Chemical Evolution Over the Pacific Airborne Mission (TRACE-P)

    NASA Technical Reports Server (NTRS)

    Talbot, Robert W.; Dibb, Jack E.

    2004-01-01

    The UNH investigation during TRACE-P provided measurements of selected acidic gases and aerosol species aboard the NASA DC-8 research aircraft. Our investigation focused on measuring HNO3, SO2, and fine (less than 2 microns) aerosol SO4(sup 2-) with two minute time resolution in near-real-time. We also quantified mixing ratios of aerosol ionic species, and aerosol (210)Pb and (7)Be collected onto bulk filters at better than 10 minute resolution. This suite of measurements contributed extensively to achieving the principal objectives of TRACE-P. In the context of the full data set collected by experimental teams on the DC-8, our observations provide a solid basis for assessing decadal changes in the chemical composition and source strength of Asian continental outflow. This region of the Pacific should be impacted profoundly by Asian emissions at this time with significant degradation of air quality over the next few decades. Atmospheric measurements in the western Pacific region will provide a valuable time series to help quantify the impact of Asian anthropogenic activities. Our data also provide important insight into the chemical and physical processes transforming Asian outflow during transport over the Pacific, particularly uptake and reactions of soluble gases on aerosol particles. In addition, the TRACE-P data set provide strong constraints for assessing and improving the chemical fields simulated by chemical transport models.

  12. Calculation of the solubility diagrams in the system Ca(OH) 2-H 3PO 4-KOH-HNO 3-CO 2-H 2O

    NASA Astrophysics Data System (ADS)

    Vereecke, Guy; Lemaître, Jacques

    1990-09-01

    A computer program has been developed for calculating the solubility isotherms of sparingly soluble calcium phosphates (including octacalcium phosphate and β-tricalcium phosphate) and calcite in the system Ca(OH) 2-H 3PO 4-KOH-HNO 3-CO 2-H 2O. It allows the influence of such parameters as temperature, pH, partial CO 2 pressure and ionic strength to be investigated. The calculation process takes into account the effects of ion-pair formation and ionic strength. Selected solubility isotherms are presented and compared to literature data. The influence of temperature, Ca/P ratio, ionic strength and CO 2 pressure on the stability isotherms of hydroxyapatite and dicalcium phosphate are discussed in detail.

  13. HCl Vapour Pressures and Reaction Probabilities for ClONO2 + HCl on Liquid H2SO4-HNO3-HCl-H20 Solutions

    NASA Technical Reports Server (NTRS)

    Elrod, M. J.; Koch, R. E.; Kim, J. E.; Molina, M. J.

    1995-01-01

    Henry's Law solubility constants for HCl have been measured for liquid H2SO4-HNO3-HCl-H2O solutions; the results are in good agreement with predictions from published semiempirical models. The ClONO2 + HCl reaction on the surfaces of such solutions with compositions simulating those of stratospheric aerosols has been investigated; as the composition changes following the temperature drop characteristic of the high-latitude stratosphere the reaction probability gamma increases rapidly. Furthermore, the gamma values remain essentially unchanged when HN03 uptake is neglected; the controlling factor appears to be the solubility of HCl. These results corroborate our earlier suggestion that supercooled liquid sulfate aerosols promote chlorine activation at low temperatures as efficiently as solid polar stratospheric cloud particles.

  14. Studies of single aerosol particles containing malonic acid, glutaric acid, and their mixtures with sodium chloride. II. Liquid-state vapor pressures of the acids.

    PubMed

    Pope, Francis D; Tong, Hai-Jie; Dennis-Smither, Ben J; Griffiths, Paul T; Clegg, Simon L; Reid, Jonathan P; Cox, R Anthony

    2010-09-23

    The vapor pressures of two dicarboxylic acids, malonic acid and glutaric acid, are determined by the measurement of the evaporation rate of the dicarboxylic acids from single levitated particles. Two laboratory methods were used to isolate single particles, an electrodynamic balance and optical tweezers (glutaric acid only). The declining sizes of individual aerosol particles over time were followed using elastic Mie scattering or cavity enhanced Raman scattering. Experiments were conducted over the temperature range of 280-304 K and a range of relative humidities. The subcooled liquid vapor pressures of malonic and glutaric acid at 298.15 K were found to be 6.7(-1.2)(+2.6) x 10(-4) and 11.2(-4.7)(+9.6) x 10(-4) Pa, respectively, and the standard enthalpies of vaporization were respectively 141.9 ± 19.9 and 100.8 ± 23.9 kJ mol(-1). The vapor pressures of both glutaric acid and malonic acid in single particles composed of mixed inorganic/organic composition were found to be independent of salt concentration within the uncertainty of the measurements. Results are compared with previous laboratory determinations and theoretical predictions.

  15. Acute generalized exanthematous pustulosis (AGEP) due to exposure to sulfuric acid and bromic acid vapor: a case report.

    PubMed

    Bilac, Dilek Bayraktar; Ermertcan, Aylin Turel; Ozturkcan, Serap; Sahin, M Turhan; Temiz, Peyker

    2008-01-01

    Acute generalized exanthematous pustulosis (AGEP, toxic pustuloderma, pustular drug eruption) is a not uncommon cutaneous reaction pattern that is usually related to drug administration. The eruption is of sudden onset and appears 7-10 days after the medication is started. A 22-year-old male patient who was a student at a chemical faculty attended our outpatient clinic with a complaint of pustular eruption on his face. According to his history, the eruption started with pruritus and erythema on his chin 3 days ago and spread to his face and chest. He explained that he had performed an experiment with sulfuric acid and bromic acid and was exposed to their vapor. His dermatological examination revealed erythema and pustules on his cheeks, on his chin, above his upper lip, and on his eyebrows. He also had a few pustules on his chest. There were no ocular, mucous membrane, or pulmonary symptoms. Histopathological examination of the skin biopsy specimen revealed superficial orthokeratosis, focal subcorneal pustule formation, and perivascular chronic inflammatory cell infiltration in superficial dermis. After administration of systemic antihistamines and wet dressing topically, we observed rapid healing of the lesions. Because there was no systemic drug intake in his history, we were concerned that exposure to sulfuric acid and bromic acid vapor caused AGEP in this patient. We present this rare case to show that the vapor of chemical materials may cause AGEP or other drug eruptions.

  16. Redistribution of nitric acid in the Arctic lower stratosphere during the winter of 1996-1997

    NASA Astrophysics Data System (ADS)

    Irie, H.; Koike, M.; Kondo, Y.; Bodeker, G. E.; Danilin, M. Y.; Sasano, Y.

    2001-10-01

    Vertical profiles of HNO3, N2O, O3, and the aerosol extinction coefficient at 780 nm were observed by the Improved Limb Atmospheric Spectrometer (ILAS) on board the Advanced Earth Observing Satellite (ADEOS) during the Arctic winter of 1996-1997. Irreversible redistribution of HNO3 is evaluated using HNO3-N2O and HNO3-O3 correlations. Denitrification and nitrification started to be observed just after the Arctic vortex cooled to below the ice frost point (TICE) on February 10. Trajectory analyses show that denitrification occurred only in air masses, which were once cooled to near TICE and were kept at temperatures below the nitric acid trihydrate saturation threshold continuously for more than 4 days. Such a temperature history provides the necessary conditions for nucleation and growth of particles causing denitrification. The average extent of denitrification at 19 km reached 43% at the center of the vortex, suggesting that stratospheric ozone could be affected by denitrification deep inside the vortex. Denitrification (>2 ppbv) and nitrification (>1 ppbv) covered 40±10% and 35±10% of the vortex area, respectively. Redistributed numbers of HNO3 molecules at each altitude were calculated by integrating the area-weighted changes in the HNO3 concentration. The decreases in total HNO3 concentration at 17-21 km in late February and early March agreed with the increases at 12-15 km to within 25%, confirming conservation of HNO3 during sedimentation and evaporation of HNO3-containing polar stratospheric cloud particles.

  17. An intercomparison of measurement systems for vapor and particulate phase concentrations of formic and acetic acids

    NASA Technical Reports Server (NTRS)

    Keene, William C.; Talbot, Robert W.; Andreae, Meinrat O.; Beecher, Kristene; Berresheim, Harold

    1989-01-01

    During June 1986, eight systems for measuring vapor phase and four for measuring particulate phase concentrations of formic acid (HCOOH) and acetic acid (CH3COOH) were intercompared in central Virginia. HCOOH and CH3COOH vapors were sampled by condensate, mist, Chromosorb 103 GC resin, NaOH-coated annular denuders, NaOH-impregnated quartz filters, K2CO3 and NaCO3-impregnated cellulose filters, and Nylasorb membranes. Atmospheric aerosol was collected on Teflon and Nuclepore filters using both hi-vol and lo-vol systems to measure particulate phase concentrations. Performances of the mist chamber and K2CO3-impregnated filter techniques were evaluated using zero air and ambient air spiked with HCOOH(g) and CH3COOH(g), and formaldehyde from permeation sources. The advantages and drawbacks of these methods are reported and discussed.

  18. The variation of nitric acid vapor and nitrate aerosol concentrations near the island of Hawaii

    SciTech Connect

    Lee, G.

    1992-01-01

    Anthropogenic emissions of nitrogen oxides (NO + NO[sub 2]) are estimated to be half of the global emissions to the atmosphere. To understand the effect of increasing anthropogenic reactive nitrogen inputs to the global atmosphere, one needs to monitor their long-term variations. This dissertation examines the variations of total nitrate (nitric acid vapor and nitrate aerosol) at the Mauna Loa Observatory (MLO), Hawaii. During the Mauna Loa Observatory Photochemistry Experiment (MLOPEX) in May, 1988, six different air types were identified at MLO with statistical analysis. They were: (1) volcano influenced air, (2) stratosphere-like air, (3) boundary-layer air with recent anthropogenic influence, (4) photochemical haze, (5) marine boundary-layer air, (6) well-aged and modified marine air. Samples that might be influenced by marine air or human activity from local islands were eliminated with three meterological criteria (wind direction, condensation nuclei, and dew point). To examine the negative sampling artifacts of nitric acid vapor due to ground loss, mixing ratio gradients with height were measured during August of 1991. The observed gradients of nitric acid vapor indicated that the long-term samplers at 8 m at MLO may underestimate the free tropospheric nitric acid vapor mixing ratio by about 20%. The three year mean and median of free tropospheric total nitrate during long-term measurements were 113 pptv and 93 pptv, respectively. Each year, the total nitrate mixing ratios at MLO during the spring and summer were increased by more than a factor of two higher than fall and winter. NO[sub y] from remote continents (Asia and North America) are likely sources of these increased total nitrate at MLO during these seasons. However, other processes govern the total nitrate mixing ratios, e.g., degree of mixing between free tropospheric air and boundary air at source regions, stratospheric injection, and wet removal of total nitrate.

  19. The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol

    NASA Astrophysics Data System (ADS)

    Stemmler, K.; Vlasenko, A.; Guimbaud, C.; Ammann, M.

    2008-01-01

    Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO3), an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO3 on deliquesced NaCl aerosol was measured in a flow reactor using HNO3 labelled with the short-lived radioactive isotope 13N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO3(g). The uptake coefficient was reduced by a factor of 5-50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond) had a detectable effect on the rate of HNO3 uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO3 uptake. Fatty acids (C18 and C15), which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO3 uptake, while monolayers of shorter-chain fatty acids (C9, C12) and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO3 uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO3 uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.

  20. The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol

    NASA Astrophysics Data System (ADS)

    Stemmler, K.; Vlasenko, A.; Guimbaud, C.; Ammann, M.

    2008-09-01

    Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO3), an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO3 on deliquesced NaCl aerosol was measured in a flow reactor using HNO3 labelled with the short-lived radioactive isotope 13N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO3(g). The uptake coefficient was reduced by a factor of 5 50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond) had a detectable effect on the rate of HNO3 uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO3 uptake. Fatty acids (C18 and C15), which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO3 uptake, while monolayers of shorter-chain fatty acids (C9, C12) and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO3 uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO3 uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.

  1. Effect of ZSM-5 Acidity on Aromatic Product Selectivity during Upgrading of Pine Pyrolysis Vapors

    SciTech Connect

    Engtrakul, Chaiwat; Mukarakate, Calvin; Starace, Anne K.; Magrini, Kimberly A.; Rogers, Allyson K.; Yung, Matthew M.

    2016-07-01

    The impact of catalyst acidity on the selectivity of upgraded biomass pyrolysis products was studied by passing pine pyrolysis vapors over five ZSM-5 catalysts of varying acidity at 500 degrees C. The SiO2-to-Al2O3 ratio (SAR) of the ZSM-5 zeolite was varied from 23 to 280 to control the acidity of the catalyst and the composition of upgraded products. The upgraded product stream was analyzed by GCMS. Additionally, catalysts were characterized using temperature programmed desorption, diffuse-reflectance FTIR spectroscopy, N2 physisorption, and X-ray diffraction. The results showed that the biomass pyrolysis vapors were highly deoxygenated to form a slate of aromatic hydrocarbons over all of the tested ZSM-5 catalysts. As the overall acidity of the ZSM-5 increased the selectivity toward alkylated (substituted) aromatics (e.g., xylene, dimethyl-naphthalene, and methyl-anthracene) decreased while the selectivity toward unsubstituted aromatics (e.g., benzene, naphthalene, and anthracene) increased. Additionally, the selectivity toward polycyclic aromatic compounds (2-ring and 3-ring) increased as catalyst acidity increased, corresponding to a decrease in acid site spacing. The increased selectivity toward less substituted polycyclic aromatic compounds with increasing acidity is related to the relative rates of cyclization and alkylation reactions within the zeolite structure. As the acid site concentration increases and sites become closer to each other, the formation of additional cyclization products occurs at a greater rate than alkylated products. The ability to adjust product selectivity within 1-, 2-, and 3-ring aromatic families, as well as the degree of substitution, by varying ZSM-5 acidity could have significant benefits in terms creating a slate of upgraded biomass pyrolysis products to meet specific target market demands.

  2. Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors

    DOE PAGES

    Engtrakul, Chaiwat; Mukarakate, Calvin; Starace, Anne K.; ...

    2015-11-14

    The impact of catalyst acidity on the selectivity of upgraded biomass pyrolysis products was studied by passing pine pyrolysis vapors over five ZSM-5 catalysts of varying acidity at 500 degrees C. The SiO2-to-Al2O3 ratio (SAR) of the ZSM-5 zeolite was varied from 23 to 280 to control the acidity of the catalyst and the composition of upgraded products. The upgraded product stream was analyzed by GCMS. Additionally, catalysts were characterized using temperature programmed desorption, diffuse-reflectance FTIR spectroscopy, N2 physisorption, and X-ray diffraction. The results showed that the biomass pyrolysis vapors were highly deoxygenated to form a slate of aromatic hydrocarbonsmore » over all of the tested ZSM-5 catalysts. As the overall acidity of the ZSM-5 increased the selectivity toward alkylated (substituted) aromatics (e.g., xylene, dimethyl-naphthalene, and methyl-anthracene) decreased while the selectivity toward unsubstituted aromatics (e.g., benzene, naphthalene, and anthracene) increased. Additionally, the selectivity toward polycyclic aromatic compounds (2-ring and 3-ring) increased as catalyst acidity increased, corresponding to a decrease in acid site spacing. The increased selectivity toward less substituted polycyclic aromatic compounds with increasing acidity is related to the relative rates of cyclization and alkylation reactions within the zeolite structure. As the acid site concentration increases and sites become closer to each other, the formation of additional cyclization products occurs at a greater rate than alkylated products. The ability to adjust product selectivity within 1-, 2-, and 3-ring aromatic families, as well as the degree of substitution, by varying ZSM-5 acidity could have significant benefits in terms creating a slate of upgraded biomass pyrolysis products to meet specific target market demands.« less

  3. Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors

    SciTech Connect

    Engtrakul, Chaiwat; Mukarakate, Calvin; Starace, Anne K.; Magrini, Kimberly A.; Rogers, Allyson K.; Yung, Matthew M.

    2015-11-14

    The impact of catalyst acidity on the selectivity of upgraded biomass pyrolysis products was studied by passing pine pyrolysis vapors over five ZSM-5 catalysts of varying acidity at 500 degrees C. The SiO2-to-Al2O3 ratio (SAR) of the ZSM-5 zeolite was varied from 23 to 280 to control the acidity of the catalyst and the composition of upgraded products. The upgraded product stream was analyzed by GCMS. Additionally, catalysts were characterized using temperature programmed desorption, diffuse-reflectance FTIR spectroscopy, N2 physisorption, and X-ray diffraction. The results showed that the biomass pyrolysis vapors were highly deoxygenated to form a slate of aromatic hydrocarbons over all of the tested ZSM-5 catalysts. As the overall acidity of the ZSM-5 increased the selectivity toward alkylated (substituted) aromatics (e.g., xylene, dimethyl-naphthalene, and methyl-anthracene) decreased while the selectivity toward unsubstituted aromatics (e.g., benzene, naphthalene, and anthracene) increased. Additionally, the selectivity toward polycyclic aromatic compounds (2-ring and 3-ring) increased as catalyst acidity increased, corresponding to a decrease in acid site spacing. The increased selectivity toward less substituted polycyclic aromatic compounds with increasing acidity is related to the relative rates of cyclization and alkylation reactions within the zeolite structure. As the acid site concentration increases and sites become closer to each other, the formation of additional cyclization products occurs at a greater rate than alkylated products. The ability to adjust product selectivity within 1-, 2-, and 3-ring aromatic families, as well as the degree of substitution, by varying ZSM-5 acidity could have significant benefits in terms creating a slate of upgraded biomass pyrolysis products to meet specific target market demands.

  4. Reduction of PCDDs/PCDFs in MSWI fly ash using microwave peroxide oxidation in H2SO4/HNO3 solution.

    PubMed

    Chang, Yu-Min; Dai, Wen-Chien; Tsai, Kao-Shen; Chen, Shiao-Shing; Chen, Jyh-Herng; Kao, Jimmy C M

    2013-05-01

    Microwave peroxide oxidation (MPO) is an energy-efficient and low GHG emission technology to destroy the hazardous organic compounds in solid waste. The objective of this paper is to explore the reduction feasibility of PCDDs/Fs in MSWI fly ash using the MPO in H2SO4/HNO3 solution. Nearly all PCDDs/Fs, 99% in the original fly ash, can be reduced in 120min at the temperature of 150°C using the MPO treatment. It was also found that a change occurred in the content distribution profiles of 17 major PCDD/F congeners before and after MPO treatment. This provides the potential to reduce the actual PCDDs/Fs content more than I-TEQ contents of PCDDs/Fs. The percentile distribution profile has a tendency of higher chlorinated PCDDs/Fs moving to the lower ones. It concludes that a significant reduction efficiency of I-TEQ toxicity was achieved and showed sufficient reduction of toxic level to lower than 1.0ngI-TEQ(gdw)(-1). The treatment temperature would be a critical factor facilitating the dissolution because higher temperature leads more inorganic salt (parts of fly ash) dissolution. Some problems caused by the MPO method are also delineated in this paper.

  5. Electrospinning of porphyrin/polyvinyl alcohol (PVA) nanofibers and their acid vapor sensing capability.

    PubMed

    Jang, Kihun; Baek, Il Woong; Back, Sung Yul; Ahn, Heejoon

    2011-07-01

    Fluorescing 5,10,15,20-terakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP)-embedded and -coated polyvinyl alcohol (PVA) nanofibers were fabricated by using the electrospinning technique. To improve nonpolar solvent solubility of TMPyP/PVA nanofibers, tetraethyl orthosilicate (TEOS) was used as a cross-linking agent. UV-vis spectroscopy showed a strong Q band and two relatively weak Soret bands from the TMPyP/PVA nanofibers, and revealed that the TMPyP molecules were homogeneously loaded to the fibers. Scanning electron microscopy revealed that the electrospun nanofibers had ultrafine structures with an average diameter of ca. 250 nm. X-ray photoelectron spectroscopy confirmed the compositional structure of TMPyP/PVA/TEOS nanofibers and revealed the relative coverage of TMPyP molecules on the surface of TMPyP-embedded and TMPyP-coated PVA/TEOS fibers. For the comparison of the acid vapor sensitivity, TMPyP-embedded PVA/TEOS films, and TMPyP-embedded PVA/TEOS fibers, TMPyP-coated PVA/TEOS fibers were exposed to 1N nitric-acid vapor for 20-60 seconds. Fluorescence microscopy revealed that TMPyP-coated PVA/TEOS nanofibers exhibited better acid-sensing capability than TMPyP-embedded PVA/TEOS nanofibers and films.

  6. Strong Fluorescent Smart Organogel as a Dual Sensing Material for Volatile Acid and Organic Amine Vapors.

    PubMed

    Xue, Pengchong; Yao, Boqi; Wang, Panpan; Gong, Peng; Zhang, Zhenqi; Lu, Ran

    2015-11-23

    An L-phenylalanine derivative (C12PhBPCP) consisting of a strong emission fluorophore with benzoxazole and cyano groups is designed and synthesized to realize dual responses to volatile acid and organic amine vapors. The photophysical properties and self-assembly of the said derivative in the gel phase are also studied. C12PhBPCP can gelate organic solvents and self-assemble into 1 D nanofibers in the gels. UV/Vis absorption spectral results show H-aggregate formation during gelation, which indicates strong exciton coupling between fluorophores. Both wet gel and xerogel emit strong green fluorescence because the cyano group suppresses fluorescence quenching in the self-assemblies. Moreover, the xerogel film with strong green fluorescence can be used as a dual chemosensor for quantitative detection of volatile acid and organic amine vapors with fast response times and low detection limits owing to its large surface area and amplified fluorescence quenching. The detection limits are 796 ppt and 25 ppb for gaseous aniline and trifluoroacetic acid (TFA), respectively.

  7. The effect of heat treatment on the corrosion resistance of 440C stainless steel in 20% HNO3 + 2.5% Na2Cr2O7 solution

    NASA Astrophysics Data System (ADS)

    Savas, Terence P.; Wang, Allen Yi-Lan; Earthman, James C.

    2003-04-01

    The effect of heat treatment on the corrosion resistance of 440C stainless steel was investigated in a 20% HNO3 + 2.5% Na2Cr2O7 solution using electrochemical noise (ECN) measurements, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) examinations. The noise resistance ( Rn), which has been found to be inversely related to the localized corrosion rate, was measured to be 5.7E + 08 Ω-cm2, 4.2E + 08 Ω-cm2, and 3.7E + 04 Ω-cm2 for the oil-quenched, air-quenched, and vacuum furnace cooled (VFC) samples, respectively, after 1200 s exposures. The Rn for all heat treat conditions stabilized within a range of 1.0E + 07 Ω-cm2 to 3.2E + 08 Ω-cm2 after 2 h exposures. The EIS response showed a polarization resistance ( R p) on the order of 6.6E + 04 Ω-cm2, 5.3E + 04 Ω-cm2, and 1.1E + 04 Ω-cm2 for the oil-quenched, air-quenched, and VFC samples, respectively, after 2 h exposures. The EIS data are in good agreement with ECN data and indicate that after longer exposures, general corrosion mechanisms dominate and the corrosion rates are comparable. SEM examinations of specimens subjected to 1200 s exposures revealed that severity of pitting and intergranular corrosion damage was consistent with trends in the Rn data. Specifically, the electrochemical noise data as well as SEM examinations of specimens revealed a higher localized corrosion resistance of the hardened specimens during the early stages of passivation. This greater resistance to localized corrosion can be attributed to an increased stability of the natural passive film resulting from a higher concentration of chromium atoms in solution for the martensite phase.

  8. Simulating the phase partitioning of NH3, HNO3, and HCl with size-resolved particles over northern Colorado in winter

    NASA Astrophysics Data System (ADS)

    Kelly, James T.; Baker, Kirk R.; Nolte, Christopher G.; Napelenok, Sergey L.; Keene, William C.; Pszenny, Alexander A. P.

    2016-04-01

    Numerical modeling of inorganic aerosol processes is useful in air quality management, but comprehensive evaluation of modeled aerosol processes is rarely possible due to the lack of comprehensive datasets. During the Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) campaign in February and March 2011, the phase partitioning of soluble trace gases with size-resolved particles and related meteorological conditions were measured continuously at a site in Colorado about 33 km north of Denver. These size-resolved measurements of particulate SO42-, NH4+, NO3-, Cl-, Na+, Ca2+, Mg2+, and K+ and inorganic gases are used here to assess the ability of a continental U.S. modeling platform to simulate the gas-particle partitioning of NH3, HNO3, and HCl at this location. Modeling is based on the Community Multiscale Air Quality (CMAQ) model with 12 km horizontal resolution. Baseline, sensitivity, and source apportionment simulations are conducted to fully characterize the model predictions. Considering the limitations in representing regional terrain features in the national 12 km modeling, predictions agree reasonably well with measured concentrations and gas-particle partitioning at this location. However, the median sum of NH4+ and NH3 is underpredicted in the baseline simulation by a factor of four suggesting a need for improved bottom-up NH3 emissions inventories in this area. The median sum of Cl- and HCl is underpredicted by a factor of 2.8, while levels of Ca2+, Mg2+, and K+ are overpredicted. Improvements in windblown and fugitive dust emissions may improve and/or better constrain these predictions. Mass size distributions for inorganic particle constituents are generally simulated well, although the modeled fine particle mode is shifted to slightly larger diameters relative to measurements. Source apportionment modeling estimates of source sector and boundary contributions to air quality at the site are provided.

  9. An Investigation of Solid-State Amidization and Imidization Reactions in Vapor Deposited Poly (amic acid)

    SciTech Connect

    Anthamatten, M; Letts, S A; Day, K; Cook, R C; Gies, A P; Hamilton, T P; Nonidez, W K

    2004-06-28

    The condensation polymerization reaction of 4,4'-oxydianiline (ODA) with pyromellitic dianhydride (PMDA) to form poly(amic acid) and the subsequent imidization reaction to form polyimide were investigated for films prepared using vapor deposition polymerization techniques. Fourier-transform infrared spectroscopy (FT-IR), thermal analysis, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) of films at different temperatures indicate that additional solid-state polymerization occurs prior to imidization reactions. Experiments reveal that, upon vapor deposition, poly(amic acid) oligomers form that have a number-average molecular weight of about 1500 Daltons. Between 100 - 130 C these chains undergo additional condensation reaction to form slightly higher molecular weight oligomers. Calorimetry measurements show that this reaction is exothermic ({Delta}H {approx} -30 J/g) with an activation energy of about 120 kJ/mol. Experimental reaction enthalpies are compared to results from ab initio molecular modeling calculations to estimate the number of amide groups formed. At higher temperatures (150 - 300 C) imidization of amide linkages occurs as an endothermic reaction ({Delta}H {approx} +120 J/g) with an activation energy of about 130 kJ/mol. Solid-state kinetics were found to depend on reaction conversion as well as the processing conditions used to deposit films.

  10. Vapor Phase Dehydration of Glycerol to Acrolein Over SBA-15 Supported Vanadium Substituted Phosphomolybdic Acid Catalyst.

    PubMed

    Viswanadham, Balaga; Srikanth, Amirineni; Kumar, Vanama Pavan; Chary, Komandur V R

    2015-07-01

    Vapor phase dehydration of glycerol to acrolein was investigated over heteropolyacid (HPA) catalysts containing vanadium substituted phosphomolybdic acid (H4PMo11VO40) supported on mesoporous SBA-15. A series of HPA catalysts with HPA loadings varying from 10-50 wt% were prepared by impregnation method on SBA-15 support. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, Fourier Transform infrared spectroscopy, temperature-programmed desorption of NH3, pyridine adsorbed FT-IR spectroscopy, scanning electron microscopy, pore size distribution and specific surface area measurements. The nature of acidic sites was examined by pyridine adsorbed FT-IR spectroscopy. XRD results suggest that the active phase containing HPA was highly dispersed at lower loadings on the support. FT-IR and Raman spectra results confirm that the presence of primary Keggin ion structure of HPA on the support and it was not affected during the preparation of catalysts. Pore size distribution results reveal that all the samples show unimodel pore size distribution with well depicted mesoporous structure. NH3-TPD results suggest that the acidity of catalysts increased with increase of HPA loading. The findings of acidity measurements by FT-IR spectra of pyridine adsorption reveals that the catalysts consist both the Brønsted and Lewis acidic sites and the amount of Brønsted acidic sites are increasing with HPA loading. SBA-15 supported vanadium substituted phosphomolybdic acid catalysts are found to be highly active during the dehydration reaction and exhibited 100% conversion of glycerol (10 wt% of glycerol) and the acrolein selectivity was appreciably changed with HPA active phase loading. The catalytic functionalities during glycerol dehydration are well correlated with surface acidity of the catalysts.

  11. Sulfuric acid vapor and other cloud-related gases in the Venus atmosphere - Abundances inferred from observed radio opacity

    NASA Technical Reports Server (NTRS)

    Steffes, P. G.; Eshleman, V. R.

    1982-01-01

    It is suggested that the absorbing characteristics of sulfuric acid vapor appear to reconcile what had been thought to be an inconsistency among measurements and deductions regarding the constituents of the Venus atmosphere and radio occultation, radar reflection, and radio emission measurements of its opacity. Laboratory measurements of sulfuric acid, sulfur dioxide, water vapor, and carbon dioxide are used to model relative contributions to opacity as a function of height in a way that is consistent with observations of the constituents and absorbing properties of the atmosphere. It is concluded that sulfuric acid vapor is likely to be the principal microwave absorber in the 30-50 km altitude range of the middle atmosphere of Venus.

  12. Vapor Hydrofluoric Acid Sacrificial Release Technique for Micro Electro Mechanical Systems Using Labware

    NASA Astrophysics Data System (ADS)

    Fukuta, Yamato; Fujita, Hiroyuki; Toshiyoshi, Hiroshi

    2003-06-01

    We have developed a novel technique of sacrificial layer etching for micro electro mechanical systems (MEMS). Our technique uses vapor of hydrofluoric acid (HF) to etch sacrificial silicon oxide and to make freestanding silicon microstructures. The advantages of this technique are: (1) no subsequent water rinse is needed, (2) freestanding silicon microstructures can be successfully released without sticking to the substrate, (3) equipment for our vapor phase HF etching simply consists of Teflon beakers only. Conditions for the technique have been optimized by estimating etching rate with test patterns made of silicon-on-insulator (SOI) wafers and by observing water droplets condensation on the sample surface with thermally oxidized silicon chips. By this technique we have successfully obtained freestanding microstructures of SOI wafers. Microcantilevers of as long as 5000 μm (a 5-μm-wide, 10-μm-thick, and 5000-μm-long cantilever over a 0.6-μm-gap) have been successfully released without adhering to the base substrate or contacting the neighboring cantilevers. We have also fabricated and actuated electrostatic comb-drive actuators of 60 and 200 comb pairs to demonstrate high processing yield of our nonstick releasing technique.

  13. SMILES zonal and diurnal variation climatology of stratospheric and mesospheric trace gasses: O3, HCl, HNO3, ClO, BrO, HOCl, HO2, and temperature

    NASA Astrophysics Data System (ADS)

    Kreyling, Daniel; Sagawa, Hideo; Wohltmann, Ingo; Lehmann, Ralph; Kasai, Yasuko

    2013-10-01

    We present a climatology of the diurnal variation of short-lived atmospheric compounds, such as ClO, BrO, HO2, and HOCl, as well as longer-lived species: O3, the hydrogen chloride isotopes H35Cl and H37Cl, and HNO3. Measurements were taken by the Superconducting Submillimeter-wave Limb-Emission Sounder (SMILES). This spectrally resolving radiometer, with very low observation noise and altitude range from the lower stratosphere to the lower thermosphere (20-100km), was measuring vertical profiles of absorption spectra along a non-sun-synchronous orbit, thus observing at all local times. We used the retrieved volume mixing ratio profiles to compile climatologies that are a function of pressure, a horizontal coordinate (latitude or equivalent latitude), and a temporal coordinate (solar zenith angle or local solar time). The main product presented are climatologies with a high resolution of the temporal coordinate (diurnal variation climatologies). In addition, we provide climatologies with a high resolution of the horizontal coordinate (zonal climatologies).The diurnal variation climatologies are based on data periods of 2 months and the zonal climatologies on monthly data periods. Consideration of the SMILES time-space sampling patterns with respect to the averaging coordinates is a key issue for climatology creation, especially in case of diurnal variation climatologies. Biases induced by inhomogeneous sampling are minimized by carefully choosing the size of averaging bins. The sampling biases of the diurnal variation climatology of ClO and BrO are investigated in a comparison of homogeneously sampled model data versus SMILES-sampled model data from the stratospheric Lagrangian chemistry and transport model Alfred Wegener Institute Lagrangian Chemisrty/Transport System. In most cases, the relative sampling error is in the range of 0-20%. The strongest impact of sampling biases is found where the species' temporal gradients are strongest (mostly at sunrise and sunset

  14. Vapor Phase Ketonization of Acetic Acid on Ceria Based Metal Oxides

    SciTech Connect

    Liu, Changjun; Karim, Ayman M.; Lebarbier, Vanessa M.; Mei, Donghai; Wang, Yong

    2013-06-27

    The activities of CeO2, Mn2O3-CeO2 and ZrO2-CeO2 were measured for acetic acid ketonization under reaction conditions relevant to pyrolysis vapor upgrading. We show that the catalyst ranking changed depending on the reaction conditions. Mn2O3-CeO2 was the most active catalyst at 350 oC, while ZrO2 - CeO2 was the most active catalyst at 450 oC. Under high CO2 and steam concentration in the reactants, Mn2O3-CeO2 was the most active catalyst at 350 and 450 °C. The binding energies of steam and CO2 with the active phase were calculated to provide the insight into the tolerance of Mn2O3-CeO2 to steam and CO2.

  15. MW Spectroscopy Coupled with Ultrafast UV Laser Vaporization: Succinic Acid in the Gas Phase

    NASA Astrophysics Data System (ADS)

    Mendez, Estibaliz; Ecija, Patricia; Cocinero, Emilio J.; Castano, Fernando; Basterretxea, Francisco J.; Godfrey, Peter D.; McNaughton, Don; Jahn, Michaela K.; Nair, K. P. Rajappan; Grabow, Jens-Uwe

    2013-06-01

    Recent lab and field measurements have indicated critical roles of organic acids in enhancing new atmospheric aerosol formation. In order to understand the nucleation process, here we report an experimental and theoretical investigation of chemical structure of succinic acid. We have used the technique of Fourier Transform Microwave Spectroscopy (FTMW). Succinic acid was vaporized by UV ultrafast laser ablation to suppress thermal decomposition processes^a and seeded into an expanding stream of Ne forming a supersonic jet. The rotational spectrum detected the presence of a single most stable conformation in the cm- mm- wave regions for which accurate rotational and centrifugal distortion parameters have been determined. The study was extended to all monosubstituted isotopic species (^{13}C, ^{18}O, D(O)), which were positively identified, leading to an accurate determination of the effective and substitution structures of the molecule. The experimental study was supplemented by ab initio (MP2) and DFT (M06-2X and B3LYP) calculations. ^{a} E. J. Cocinero, A. Lesarri, P. écija, F. J. Basterretxea, J. U. Grabow, J. A. Fernández and F. Castaño, Angew. Chem. Int. Ed., 51, 3119-3124, 2012.

  16. Measurements of tropospheric nitric acid over the Western United States and Northeastern Pacific Ocean

    NASA Technical Reports Server (NTRS)

    Lebel, P. J.; Huebert, B. J.; Schiff, H. I.; Vay, S. A.; Vanbramer, S. E.; Hastie, D. R.

    1990-01-01

    Over 240 measurements of nitric acid (HNO3) were made in the free troposphere as well as in the boundary layer. Marine HNO3 measurement results were strikingly similar to results from GAMETAG and other past atmospheric field experiments. The marine boundary layer HNO3 average, 62 parts-per-trillion by volume (pptv), was 1/3 lower than the marine free tropospheric average, 108 pptv, suggesting that the boundary layer is a sink for tropospheric nitric acid, probably by dry deposition. Nitric acid measurements on a nighttime continental flight gave a free tropospheric average of 218 pptv, substantially greater than the daytime continental free tropospheric 5-flight average of 61 pptv. However, the nighttime results may be influenced by highly convective conditions that existed from thunderstorms in the vicinity during that night flight. The continental boundary layer HNO3 average of 767 pptv is an order of magnitude greater than the free tropospheric average, indicating that the boundary layer is a source of free tropospheric HNO3. The distribution of continental boundary layer HNO3 data, from averages of 123 over rural Nevada and Utah to 1057 pptv in the polluted San Joaquin Valley of California suggest a close tie between boundary layer HNO3 and anthropogenic activity.

  17. A laboratory study of the heterogeneous reaction of nitric acid on calcium carbonate particles

    NASA Astrophysics Data System (ADS)

    Goodman, A. L.; Underwood, G. M.; Grassian, V. H.

    2000-12-01

    It has been postulated that the reaction of nitric acid with calcium carbonate, namely, CaCO3(s) + 2HNO3(g) → Ca(NO3)2(s) + CO2(g) + H2O(g), plays an important role in the atmosphere. In this study, transmission FTIR spectroscopy, diffuse reflectance UV-visible spectroscopy, transmission electron microscopy and a Knudsen cell reactor coupled to a quadrupole mass spectrometer have been used to investigate the heterogeneous reactivity of HNO3 on CaCO3 at 295 K as a function of relative humidity. Transmission FTIR spectroscopy was used to probe both gas-phase and adsorbed products and showed that the reaction of HNO3 and CaCO3 is limited to the surface of the CaCO3 particle in the absence of adsorbed water. However, in the presence of water vapor, the reaction is greatly enhanced and is not limited to the surface of the particle producing both solid calcium nitrate and gaseous carbon dioxide. The enhanced reactivity of the particles is attributed to the presence of a layer of adsorbed water on the particle surface. The amount of adsorbed water on the particle surface is strongly dependent on the extent of the reaction. This can be understood in terms of the increased hydrophilicity of calcium nitrate as compared to calcium carbonate. Data from experiments using a mass-calibrated Knudsen cell reactor showed the stoichiometry for the reaction determined from gas-phase species deviated from that expected from the balanced equation. Water adsorption on the particle surface and gases dissolved into the water layer appear to be the cause of this discrepancy. The measured uptake coefficient accounting for the BET area of the sample is determined to be 2.5±0.1×10-4 for HNO3 on CaCO3 under dry conditions and is found to increase in the presence of water vapor. Atmospheric implications of the results presented here are discussed.

  18. Unravelling the potential of nitric acid as a surface modifier for improving the hemocompatibility of metallocene polyethylene for blood contacting devices

    PubMed Central

    Vellayappan, Muthu Vignesh; Muhamad, Ida Idayu

    2016-01-01

    Design of blood compatible surfaces is obligatory to minimize platelet surface interactions and improve the thromboresistance of foreign surfaces when they are utilized as biomaterials particularly for blood contacting devices. Pure metallocene polyethylene (mPE) and nitric acid (HNO3) treated mPE antithrombogenicity and hydrophilicity were investigated. The contact angle of the mPE treated with HNO3 decreased. Surface of mPE and HNO3 treated mPE investigated with FTIR revealed no major changes in its functional groups. 3D Hirox digital microscopy, SEM and AFM images show increased porosity and surface roughness. Blood coagulation assays prothrombin time (PT) and activated partial thromboplastin time (APTT) were delayed significantly (P < 0.05) for HNO3 treated mPE. Hemolysis assay and platelet adhesion of the treated surface resulted in the lysis of red blood cells and platelet adherence, respectively indicating improved hemocompatibility of HNO3 treated mPE. To determine that HNO3 does not deteriorate elastic modulus of mPE, the elastic modulus of mPE and HNO3 treated mPE was compared and the result shows no significant difference. Hence, the overall observation suggests that the novel HNO3 treated mPE may hold great promises to be exploited for blood contacting devices like grafts, catheters, and etc. PMID:26819837

  19. Adsorption of water vapor by poly(styrenesulfonic acid), sodium salt: isothermal and isobaric adsorption equilibria.

    PubMed

    Toribio, F; Bellat, J P; Nguyen, P H; Dupont, M

    2004-12-15

    Air conditioning and dehumidifying systems based on sorption on solids are of great interest, especially in humid climates, because they allow reduction of thermal loads and use of chlorofluorocarbons. Previous studies have shown that hydrophilic polymers such as sulfonic polymers can have very high performance in water adsorption from air. The aim of this study was to characterize the water vapor adsorption properties of fully sulfonated and monosulfonated poly(styrenesulfonic acid), sodium salt, and to elucidate the mechanism of adsorption on these materials. Adsorption isotherms have been determined by TGA between 298 and 317 K for pressures ranging from 0.1 to 45 hPa. They have type II of the IUPAC classification and a small hysteresis loop between adsorption and desorption processes was observed only for the monosulfonated sample. Water content is up to 80% weight at 80% relative humidity. Adsorption isotherms have been well fitted with the FHH model. Adsorption-desorption isobars have been determined by TGA under 37 hPa in the temperature range 298-373 K. They show that these polymers can be completely regenerated by heating at 313 K under humidified air. No degradation of the adsorption properties has been observed after several regenerations. Adsorption enthalpies and entropies have been deduced from the Clapeyron equation and from DSC measurements. A good agreement was found. A mechanism of adsorption is proposed considering two kinds of adsorbate: bounded water in electrostatic interaction with functional groups and free water resulting from condensation.

  20. Improvements in the profiles and distributions of nitric acid and nitrogen dioxide with the LIMS version 6 dataset

    NASA Astrophysics Data System (ADS)

    Remsberg, E.; Natarajan, M.; Marshall, T.; Gordley, L. L.; Thompson, R. E.; Lingenfelser, G.

    2010-02-01

    The quality of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) nitric acid (HNO3) and nitrogen dioxide (NO2) profiles and distributions of 1978/1979 is described after their processing with an updated, Version 6 (V6) algorithm and subsequent archival in 2002. Estimates of the precision and accuracy of both of those species are developed and provided herein. The character of the V6 HNO3 profiles is relatively unchanged from that of the earlier LIMS Version 5 (V5) profiles, except in the upper stratosphere where the interfering effects of CO2 are accounted for better with V6. The accuracy of the retrieved V6 NO2 is also significantly better in the middle and upper stratosphere, due to improvements in its spectral line parameters and in the reduced biases for the accompanying V6 temperature and water vapor profiles. As a result of these important updates, there is better agreement with theoretical calculations for profiles of the HNO3/NO2 ratio, day-to-night NO2 ratio, and with estimates of the production of NO2 in the mesosphere and its descent to the upper stratosphere during polar night. The improved precisions and more frequent retrievals of the profiles along the LIMS orbit tracks provide for better continuity and detail in map analyses of these two species on pressure surfaces. It is judged that the chemical effects of the oxides of nitrogen on ozone can be examined quantitatively throughout the stratosphere with the LIMS V6 data, and that the findings will be more compatible with those obtained from measurements of the same species from subsequent satellite sensors.

  1. Improvements in the profiles and distributions of nitric acid and nitrogen dioxide with the LIMS version 6 dataset

    NASA Astrophysics Data System (ADS)

    Remsberg, E.; Natarajan, M.; Marshall, B. T.; Gordley, L. L.; Thompson, R. E.; Lingenfelser, G.

    2010-05-01

    The quality of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) nitric acid (HNO3) and nitrogen dioxide (NO2) profiles and distributions of 1978/1979 are described after their processing with an updated, Version 6 (V6) algorithm and subsequent archival in 2002. Estimates of the precision and accuracy of both of those species are developed and provided herein. The character of the V6 HNO3 profiles is relatively unchanged from that of the earlier LIMS Version 5 (V5) profiles, except in the upper stratosphere where the interfering effects of CO2 are accounted for better with V6. The accuracy of the retrieved V6 NO2 is also significantly better in the middle and upper stratosphere, due to improvements in its spectral line parameters and in the reduced biases for the accompanying V6 temperature and water vapor profiles. As a result of these important updates, there is better agreement with theoretical calculations for profiles of the HNO3/NO2 ratio, day-to-night NO2 ratio, and with estimates of the production of NO2 in the mesosphere and its descent to the upper stratosphere during polar night. In particular, the findings for middle and upper stratospheric NO2 should also be more compatible with those obtained from more recent satellite sensors because the effects of the spin-splitting of the NO2 lines are accounted for now with the LIMS V6 algorithm. The improved precisions and more frequent retrievals of the LIMS profiles along their orbit tracks provide for better continuity and detail in map analyses of these two species on pressure surfaces. It is judged that the chemical effects of the oxides of nitrogen on ozone can be studied quantitatively throughout the stratosphere with the LIMS V6 data.

  2. An Investigation of the Solid-State Condensation Polymerization Reaction in Vapor-Deposited Poly(amic acid)

    NASA Astrophysics Data System (ADS)

    Anthamatten, Mitchell; Letts, Stephan A.; Day, Katherine; Cook, Robert C.; Gies, Anthony P.; Nonidez, William K.

    2004-03-01

    The condensation polymerization reaction of 4,4'-oxydianiline (ODA) with pyromellitic dianhydride (PMDA) to form poly(amic acid) and the subsequent imidization reaction to form polyimide were investigated for films prepared using vapor deposition polymerization techniques. Fourier-transform infrared spectroscopy (FTIR), thermal analysis, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of films prepared at different temperatures indicate that additional solid-state polymerization occurs prior to imidization reactions. Experiments suggest that poly(amic acid) oligomers form upon vapor-deposition and have a number-average molecular weights of about 1500 Daltons. Between 100-130 °C these chains undergo additional condensation reactions to form slightly higher molecular weight oligomers. This work was performed under the auspices of the U.S. Department of Energy by the University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

  3. On the acidity of dew

    NASA Astrophysics Data System (ADS)

    Pierson, William R.; Brachaczek, Wanda W.; Gorse, Robert A.; Japar, Steven M.; Norbeck, Joseph M.

    1986-03-01

    Nightly dew samples were collected on Allegheny Mountain in southwest Pennsylvania in August 1983. The dew was found to be acidic, with mean pH˜4.0. Free H+ comprised >80% of the total acidity, and the composition approximated an H2SO4/HNO3 mixture with average SO42-/NO3- mol ratio ˜1.3. The chemistry of the dew resembled that of rain at Allegheny, though the dew was generally more dilute. Atmospheric HNO3(g) was chiefly responsible for the dew NO3-. SO2 was the source of ˜80% of the dew SO42-. The allocation of dew H+ among atmospheric precursors was HNO3˜30%, SO2 ≥ 60%, aerosol H+ ≤ 10%. The most acidic dews were associated with wind from the west. Average deposition velocities (stated in centimeters per second) to dew were HNO3, 0.24; NO2, <0.02 SO2, ˜0.04; aerosol SO42-, ˜0.02; aerosol NH4+, 0.024; and aerosol species, 0.02-1. Comparison of the HNO3 deposition velocity with ten-fold higher summer daytime values reveals a pronounced diurnal variation. The 0.24 cm/s value for HNO3 may represent a maximum for any gas or submicron aerosol species whenever the atmosphere is strongly stable. Not all of the S(IV) in dew had been converted to SO42- by morning; thus the rate of oxidation must have been on a time scale of hours at nighttime ambient temperatures. In contrast, S(IV) in rain and fog samples was not evident. Deposition fluxes and cumulative deposition totals involving dew, rain, and settled fog water were compared. Rain proved by far the most important for deposition of all solute species, including acid.

  4. Acidity of vapor plume from cooling tower mixed with flue gases emitted from coal-fired power plant.

    PubMed

    Hlawiczka, Stanislaw; Korszun, Katarzyna; Fudala, Janina

    2016-06-01

    Acidity of products resulting from the reaction of flue gas components emitted from a coal-fired power plant with water contained in a vapor plume from a wet cooling tower was analyzed in a close vicinity of a power plant (710 m from the stack and 315 m from the cooling tower). Samples of this mixture were collected using a precipitation funnel where components of the mixed plumes were discharged from the atmosphere with the rainfall. To identify situations when the precipitation occurred at the same time as the wind directed the mixed vapor and flue gas plumes above the precipitation funnel, an ultrasound anemometer designed for 3D measurements of the wind field located near the funnel was used. Precipitation samples of extremely high acidity were identified - about 5% of samples collected during 12 months showed the acidity below pH=3 and the lowest recorded pH was 1.4. During the measurement period the value of pH characterizing the background acidity of the precipitation was about 6. The main outcome of this study was to demonstrate a very high, and so far completely underestimated, potential of occurrence of episodes of extremely acid depositions in the immediate vicinity of a coal-fired power plant.

  5. Topochemical diffusion-reaction-convection dynamics in vapor-to-particle aerosol nucleation and growth

    NASA Astrophysics Data System (ADS)

    Thompson, Stephen; Shipman, Patrick D.

    2013-05-01

    We report on patterns and oscillations observed in topochemically organized vapor-toparticle experimental systems involving aerosol nucleation and growth processes in which NH3 reacts with HCl, HNO3, H2SO4, and CH3COOH. Mathematical models of these systems in comparison with experiments allow us to estimate parameters such as kinetic constants and nucleation thresholds. The patterns are strongly influenced by charging, hydration, and turbulence driven by exothermicity.

  6. Vapor pressures and calculated heats of vaporization of concentrated nitric acid solutions in the composition range 71 to 89 percent nitrogen dioxide, 1 to 10 percent water, and in the temperature range 10 to 60 degrees C

    NASA Technical Reports Server (NTRS)

    Mckeown, A B; Belles, Frank E

    1954-01-01

    Total vapor pressures were measured for 16 acid mixtures of the ternary system nitric acid, nitrogen dioxide, and water within the temperature range 10 degrees to 60 degrees Celsius, and with the composition range 71 to 89 weight percent nitric acid, 7 to 20 weight percent nitrogen dioxide, and 1 to 10 weight percent water. Heats of vaporization were calculated from the vapor pressure measurements for each sample for the temperatures 25, 40, and 60 degrees Celsius. The ullage of the apparatus used for the measurements was 0.46. Ternary diagrams showing isobars as a function of composition of the system were constructed from experimental and interpolated data for the temperatures 25, 40, 45, and 60 degrees C and are presented herein.

  7. Optimum condition to fabricate 5-10 nm SiO2/Si structure using advanced nitric acid oxidation of Si method with Si source

    NASA Astrophysics Data System (ADS)

    Imamura, Kentaro; Matsumoto, Taketoshi; Kobayashi, Hikaru

    2012-12-01

    A low temperature (≦120 °C) fabrication method to form relatively thick SiO2/Si structure with a Si source has been developed using the advanced nitric acid oxidation of Si (NAOS) method, and the formation mechanism has been investigated. The reaction mechanism consists of direct oxidation of Si, dissolution of Si sources, and surface reaction of the dissolved Si species. The dissolved Si species is present in HNO3 solutions as mono-silicic acid and reacts with oxidizing species formed by decomposition of HNO3 on an ultrathin SiO2 layer (i.e., 1.4 nm) produced by the direct oxidation of Si substrates with HNO3 solutions. To achieve a uniform thickness of SiO2 layer with a smooth surface, HNO3 solutions with concentrations higher than 60 wt. % are needed because the dissolved Si species polymerizes in HNO3 solutions when the concentration is below 60 wt. %, resulting in the formation of SiO2 particles in HNO3, which are deposited afterwards on the SiO2 layer. In spite of the low temperature formation at 120 °C, the electrical characteristics of the advanced NAOS SiO2 layer formed with 68 wt. % HNO3 and subsequent post-metallization anneal at 250 °C are nearly identical to those of thermal oxide formed at 900 °C.

  8. Plutonium and Americium Alpha Radiolysis of Nitric Acid Solutions.

    PubMed

    Horne, Gregory P; Gregson, Colin R; Sims, Howard E; Orr, Robin M; Taylor, Robin J; Pimblott, Simon M

    2017-02-02

    The yield of HNO2, as a function of absorbed dose and HNO3 concentration, from the α-radiolysis of aerated HNO3 solutions containing plutonium or americium has been investigated. There are significant differences in the yields measured from solutions of the two different radionuclides. For 0.1 mol dm(-3) HNO3 solutions, the radiolytic yield of HNO2 produced by americium α-decay is below the detection limit, whereas for plutonium α-decay the yield is considerably greater than that found previously for γ-radiolysis. The differences between the solutions of the two radionuclides are a consequence of redox reactions involving plutonium and the products of aqueous HNO3 radiolysis, in particular H2O2 and HNO2 and its precursors. This radiation chemical behavior is HNO3 concentration dependent with the differences between plutonium and americium α-radiolysis decreasing with increasing HNO3 concentration. This change may be interpreted as a combination of α-radiolysis direct effects and acidity influencing the plutonium oxidation state distribution, which in turn affects the radiation chemistry of the system.

  9. Vapor-pressure osmometric study of the molecular weight and aggregation tendency of a reference-soil fulvic acid

    USGS Publications Warehouse

    Marinsky, J.A.; Reddy, M.M.

    1990-01-01

    The molecular weight and aggregation tendency of a reference-soil fulvic acid in Armadale horizon Bh were determined by vapor-pressure osmometry using tetrahydrofuran and water as solvents. With tetrahydrofuran, number-average molecular weight values of 767 ?? 34 and 699 ?? 8 daltons were obtained from two separate sets of measurements. Two sets of measurements with water also yielded values within this range (754 ?? 70 daltons) provided that the fulvic acid concentration in water did not exceed 7 mg ml-1; at higher concentrations (9.1-13.7 mg ml-1) a number-average molecular weight of 956 ?? 25 daltons was resolved, providing evidence of molecular aggregation. Extension of these studies to 80% neutralized fulvic acid showed that a sizeable fraction of the sodium counter ion is not osmotically active.

  10. Reduction of nitric acid on Ag in ultrahigh vacuum: A Raman spectroscopic investigation

    NASA Astrophysics Data System (ADS)

    Zangmeister, Christopher D.; Davis, Robert J.; Mrozek, Pawel; Pemberton, Jeanne E.

    2008-07-01

    The reduction of HNO 3 on Ag as a function of temperature in ultrahigh vacuum (UHV) is studied using Raman spectroscopy and thermal desorption-mass spectrometry (TDMS). Thin layers of molecular HNO 3 are stable on the surface below 150 K, but are spontaneously reduced above 150 K with concomitant time-dependent partial desorption of products. The asymmetric nitric oxide dimer, NONO, is observed as the sole reduction product that remains on the surface based on its distinctive Raman spectral signature. The mechanism of NONO formation from HNO 3 is proposed to occur through a multistep reduction of HNO 3 on the Ag surface starting from NO3- and proceeding stepwise through NO 2 and NO2- to NO, followed by combination to form NONO in a process catalyzed by a Lewis acid, oxidized Ag species. Desorption of the majority of surface species is largely complete by 210 K.

  11. X-ray studies of the liquid/vapor interface: Water and polymer and fatty acid monolayers on water

    SciTech Connect

    Schlossman, M.L.; Schwartz, D.K.; Kawamoto, E.H.; Kellogg, G.J.; Pershan, P.S. ); Ocko, B.M. ); Kim, M.W.; Chung, T.C. . Corporate Research Labs.)

    1989-01-01

    X-ray specular reflectivity is used to study the liquid-vapor interface of pure water and of fatty acid and polymer monolayers at that interface. For the pure water surface the reflectivity was measured for three different spectrometer resolutions and simultaneous fits with only one free parameter to all of the data are in excellent agreement with the prediction of capillary wave theory for the RMS surface roughness. Diffuse scattering away from the specular condition, at wavevectors corresponding to those of the capillary waves, yields intensities and line shapes in agreement with theory with no significant adjustable parameters. Reflectivity from separate monolayers of co-poly 1, 2-butadiene/butyl alcohol (50% random substitution) and lignoceric acid (CH{sub 3}(CH{sub 2}){sub 22}COOH) at the water/vapor interface are interpreted to obtain profiles of the average electron density {rho}(z) as a function of distance z along the surface normal. For the polymer monolayer we find the following: (1) a local maximum in the electron density approximately 10% larger than that of the bulk polymer and (2) the RMS roughness of the vapor/polymer interface agrees with capillary wave theory predictions for the lower surface pressures. For the highest surface pressure the RMS roughness exceeds the value predicted by the capillary wave model. Measurements of reflectivity from a lignoceric acid monolayer, as a function of surface pressure throughout an isotherm (near room temperature), reveal the following behavior: (1) the overall thickness of the monolayer increases with increasing pressure and (2) the head groups occupy a progressively larger region along the surface normal as the pressure increases, indicating that they rearrange normal to the interface. 15 refs., 5 figs., 2 tabs.

  12. Nitric acid partitioning in cirrus clouds: a synopsis based on field, laboratory and model studies

    NASA Astrophysics Data System (ADS)

    Krämer, M.; Beuermann, J.; Schiller, C.; Grimm, F.; Arnold, F.; Peter, Th.; Meilinger, S.; Meier, A.; Hendricks, J.; Petzold, A.; Schlager, H.

    2003-02-01

    From a synopsis of field, laboratory and model studies at T>205 K as well as from the field experiments POLSTAR at T<205 K we derive a general picture of the partitioning of nitric acid (HNO3) in cirrus clouds and a new hypothesis on the uptake of HNO3 on ice particles: A substantial part of nitric acid remains in the gas phase under cirrus cloud conditions. The HNO3 removed from the gas phase is distributed between interstitial aerosol and ice particles in dependence on the temperature and ice surface, respectively. In cold cirrus clouds with small ice surface areas (T <205 K) the partitioning is strongly in favour of interstitial ternary solution particles while in warmer cirrus clouds with large ice surface areas the uptake on ice dominates. Consequently, denitrification via sedimenting ice particles may occur only in the -more frequently occurring- warm cirrus clouds The HNO3 coverage on ice is found to be different for ice particles and ice films. On ice films the coverage can increase with decreasing temperature from about 0.1 to 0.8 monolayer, while that on ice particles is found to decrease with temperature and PHNO3 from 0.1 to 0.001 monolayer. An HNO3 uptake behaviour following dissociative Langmuir isotherms where the coverage decreases for descending temperatures may explain the observations for ice particles From a comparison of the HNO3 measurements with model calculations it is found that (i) the global model of Lawrence and Crutzen (1998) overestimates the HNO3 partitioning in favour of the ice particles (ii) the Langmuir surface chemistry model of Tabazadeh et al. (1999) overestimates HNO3 coverages for temperatures ≤210 K More appropriate coverages are calculated when implementing in that model a temperature dependent function for the adsorption free energy (ΔGads (T)), which is empirically derived from the coverage measurements.

  13. Study of the liquid vapor equilibrium in the bromine-hydrobromic acid-water system

    NASA Technical Reports Server (NTRS)

    Benizri, R.; Lessart, P.; Courvoisier, P.

    1984-01-01

    A glass ebullioscope was built and at atmospheric pressure, liquid-vapor equilibria relative to the Br2-HBr-H2O system, in the concentration range of interest for evaluation of the Mark 13 cycle was studied. Measurements were performed for the brome-azeotrope (HBr-H2O) pseudo-binary system and for the ternary system at temperatures lower than 125 C and in the bromine concentration range up to 13% wt.

  14. Effect the conditions of the acid-thermal modification of clinoptilolite have on the catalytic properties of palladium-copper complexes anchored on it in the reaction of carbon monoxide oxidation

    NASA Astrophysics Data System (ADS)

    Rakitskaya, T. L.; Kiose, T. A.; Ennan, A. A.; Golubchik, K. O.; Oleksenko, L. P.; Gerasiova, V. G.

    2016-06-01

    The dependence of the physicochemical and structural-adsorption properties of natural and acid-thermal modified clinoptilolite, and of Pd(II)-Cu(II) catalysts based on them, on the duration of acid-thermal modification is investigated. The samples under study are described via XRD and thermal gravimetric (DTG and DTA) analysis, IR, DR UV-Vis, EPR spectroscopy, and water vapor adsorption. Values of both the specific surface area ( S sp) and pH of aqueous suspensions are determined. The resulting catalysts are tested in the reaction of low-temperature carbon monoxide oxidation with air oxygen. A conclusion is drawn about the nature of surface bimetallic Pd(II)-Cu(II) complexes. The greatest catalytic activity is shown by complexes based on clinoptilolite and modified with 3 M HNO3 for 0.5 and 1 h.

  15. Calorimetry Studies of Ammonia, Nitric Acid, and Ammonium Nitrate

    DTIC Science & Technology

    1979-10-01

    block nmmber) Calorimetry Heat of reaction Ammonium nitrate Heat capacity Nitric acid Heat of solution • Amonia 20. ABSTRACT r(Cmrtfe m,.re a N "no•a.•r sd...identical to the literature spectrum of W NO3. Anhydrous nitric acid was prepared by distillation of 90% HNO 3 from fuming sulfuric acid (oxides of nitrogen

  16. Energetic particle-induced enhancements of stratospheric nitric acid

    NASA Technical Reports Server (NTRS)

    Aikin, Arthur C.

    1994-01-01

    Inclusion of complete ion chemistry in the calculation of minor species production during energetic particle deposition events leads to significant enhancement in the calculated nitric acid concentration during precipitation. An ionization rate of 1.2 x 10(exp 3)/cu cm/s imposed for 1 day increases HNO3 from 3 x 10(exp 5) to 6 x 10(exp 7)/cu cm at 50 km. With an ionization rate of 600 cu cm/s, the maximum HNO3 is 3 x 10(exp 7)/cu cm. Calculations which neglect negative ions predict the nitric acid will fall during precipitation events. The decay time for converting HNO3 into odd nitrogen and hydrogen is more than 1 day for equinoctial periods at 70 deg latitude. Examination of nitric acid data should yield important information on the magnitude and frequency of charged particle events.

  17. Thermodynamic Phase And Chemical Equilibrium At 0-110°C For The H+-K+-Na+-Cl--H2O System Up To 16 Molal And The HNO3-H2O System Up To 20 Molal Using An Association-Based Pitzer Model Compatible With ASPEN Plus

    SciTech Connect

    Todd T. Nichols; Dean D. Taylor

    2003-09-01

    A status is presented of the parameterization during FY2003 of an association-based Pitzer model to simulate chemical and phase equilibria of acid-chloride-nitrate-mercury aqueous electrolyte systems at 0-100° C within the industry-standard process simulator, ASPEN Plus. Compatibility with ASPEN Plus requires that the Pitzer model used be limited to the third virial coefficient and have the values of b and a1 as originally proposed by Pitzer. Two aqueous models for 0-110° C at atmospheric pressure were parameterized in FY03. The model for the aqueous H+-K+-Na+-Cl- system is applicable for 0-16 molal, and the HNO3-H2O for 0-20 molal. An association-based Pitzer activity coefficient model is combined with Henry.s law to predict activity/osmotic coefficient and VLE. The chloride model also predicts KCl and NaCl solubility, while the nitric acid model has the unique capability of predicting extent of dissociation with an average absolute deviation of 1.43%. The association-based approach presented here extends the utility of the molality-based Pitzer model past 6 molal to predict activity/osmotic coefficients up to 16-20 molal. The association-based approach offers the additional benefits of predicting extent of dissociation and of allowing the Pitzer model to be fully utilized in commercial simulators, such as ASPEN Plus, that require accounting for association to implement Henry’s law. The Pitzer models presented here provide the chemical process simulation engineer with a superior alternative to the Electrolyte NRTL model that can easily be used in ASPEN Plus.

  18. Thermodynamic Phase And Chemical Equilibrium At 0-110 C For The H+-K+-Na+-Cl--H2O System Up To 16 Molal And The HNO3-H2O System Up To 20 Molal Using An Association-Based Pitzer Model Compatible With ASPEN Plus

    SciTech Connect

    Nichols,T.T.; Taylor,D.D.

    2003-09-26

    A status is presented of the parameterization during FY2003 of an association-based Pitzer model to simulate chemical and phase equilibria of acid-chloride-nitrate-mercury aqueous electrolyte systems at 0-100 C within the industry-standard process simulator, ASPEN Plus. Compatibility with ASPEN Plus requires that the Pitzer model used be limited to the third virial coefficient and have the values of b and a1 as originally proposed by Pitzer. Two aqueous models for 0-110 C at atmospheric pressure were parameterized in FY03. The model for the aqueous H+-K+-Na+-Cl- system is applicable for 0-16 molal, and the HNO3-H2O for 0-20 molal. An association-based Pitzer activity coefficient model is combined with Henry's law to predict activity/osmotic coefficient and VLE. The chloride model also predicts KCl and NaCl solubility, while the nitric acid model has the unique capability of predicting extent of dissociation with an average absolute deviation of 1.43%. The association-based approach presented here extends the utility of the molality-based Pitzer model past 6 molal to predict activity/osmotic coefficients up to 16-20 molal. The association-based approach offers the additional benefits of predicting extent of dissociation and of allowing the Pitzer model to be fully utilized in commercial simulators, such as ASPEN Plus, that require accounting for association to implement Henry's law. The Pitzer models presented here provide the chemical process simulation engineer with a superior alternative to the Electrolyte NRTL model that can easily be used in ASPEN Plus.

  19. Thermometric titration of acids in pyridine.

    PubMed

    Vidal, R; Mukherjee, L M

    1974-04-01

    Thermometric titration of HClO(4), HI, HNO(3), HBr, picric acid o-nitrobenzoic acid, 2,4- and 2,5-dinitrophenol, acetic acid and benzoic acid have been attempted in pyridine as solvent, using 1,3-diphenylguanidine as the base. Except in the case of 2,5-dinitrophenol, acetic acid and benzoic acid, the results are, in general, reasonably satisfactory. The approximate molar heats of neutralization have been calculated.

  20. Thermal behavior of potato starch and water-vaporization behavior of its paste controlled with amino acid and peptide-rich food materials.

    PubMed

    Sakauchi, Satoshi; Hattori, Makoto; Yoshida, Tadashi; Yagishita, Takahiro; Ito, Koichi; Akemitsu, Shin-Ichi; Takahashi, Koji

    2010-03-01

    The particular effect of 4 kinds of amino acid and peptide-rich food material (APRM) containing different charged amino acid contents on the gelatinization and retrogradation behavior of potato starch granules and on the water-vaporization behavior was analyzed by differential scanning calorimetry, rapid viscoanalysis, x-ray diffractometry, thermal gravimetry-differential thermal analysis, and pulsed NMR. APRM with a high-charged amino acid content produced unique gelatinization and retrogradation behavior in terms of an elevated gelatinization temperature, reduced viscosity, higher setback, and lower retrograded starch melting enthalpy. The recovered x-ray diffraction intensity decreased with increasing charged amino acid content. APRM with high-charged amino acid content could provide an improved paste having easy vaporization of external water in the swollen starch granules due to the reduced swelling.

  1. Determination of Water Vapor Pressure Over Corrosive Chemicals Versus Temperature Using Raman Spectroscopy as Exemplified with 85.5% Phosphoric Acid.

    PubMed

    Rodier, Marion; Li, Qingfeng; Berg, Rolf Willestofte; Bjerrum, Niels Janniksen

    2016-07-01

    A method to determine the water vapor pressure over a corrosive substance was developed and tested with 85.5 ± 0.4% phosphoric acid. The water vapor pressure was obtained at a range of temperatures from ∼25 ℃ to ∼200 ℃ using Raman spectrometry. The acid was placed in an ampoule and sealed with a reference gas (either hydrogen or methane) at a known pressure (typically ∼0.5 bar). By comparing the Raman signals from the water vapor and the references, the water pressure was determined as a function of temperature. A considerable amount of data on the vapor pressure of phosphoric acid are available in the literature, to which our results could successfully be compared. A record value of the vapor pressure, 3.40 bar, was determined at 210 ℃. The method required a determination of the precise Raman scattering ratios between the substance, water, and the used reference gas, hydrogen or methane. In our case the scattering ratios between water and reference ν1 Q-branches were found to be 1.20 ± 0.03 and 0.40 ± 0.02 for H2 and CH4, respectively.

  2. Absorption cross section for the 5νOH stretch of acetic acid and peracetic acid

    NASA Astrophysics Data System (ADS)

    Begashaw, I. G.; Collingwood, M.; Bililign, S.

    2009-12-01

    We report measurements of the absorption cross sections for the vibrational O-H stretch (5νOH) overtone transitions in glacial acetic acid and peracetic acid. The photochemistry that results from overtone excitation has been shown to lead to OH radical production in molecules containing O-H (HNO3, H2O2). In addition the overtone excitation has been observed to result in light initiated chemical reaction. A Cavity ring-down spectroscopy (CRDS) instrument comprising of an Nd:YAG pumped dye laser and 620nm high reflectivity mirrors (R=99.995%) was used to measure the cross sections. The dye laser wavelength was calibrated using water vapor spectrum and the HITRAN 2008 database. The instrument’s minimum detectable absorption is αmin =4.5 *10-9cm-1 Hz-1/2 at 2σ noise level near the peak of the absorption feature. This measurement is the first for acetic acid at this excitation level. Preliminary results for acetic acid show the peak occurs near 615nm. Procedures for separating the monomer and dimer contribution will be presented. We would like to acknowledge support from NSF award #0803016 and NOAA-EPP award #NA06OAR4810187.

  3. Determination of Activity Coefficients of di-(2-ethylhexyl) Phosphoric Acid Dimer in Select Organic Solvents Using Vapor Phase Osmometry

    SciTech Connect

    Michael F. Gray; Peter Zalupski; Mikael Nilsson

    2013-08-01

    Effective models for solvent extraction require accurate characterization of the nonideality effects for each component, including the extractants. In this study, the nonideal behavior of the industrial extractant di(2-ethylhexyl) phosphoric acid has been investigated using vapor pressure osmometry (VPO). From the osmometry data, activity coefficients for the HDEHP dimer were obtained based on a formulation of the regular solution theory of Scatchard and Hildebrand, and the Margules two- and three-suffix equations. The results show similarity with a slope-analysis based relation from previous literature, although important differences are highlighted. The work points towards VPO as a useful technique for this type of study, but care must be taken with the choice of standard and method of analysis.

  4. Electrical conductivity measurements of aqueous boric acid at 25--350{degree}C at saturation vapor pressure. Final report

    SciTech Connect

    Ho, P.C.; Palmer, D.A.

    1995-09-01

    Electrical conductance measurements of aqueous boric acid solutions (15-110 g/kg-H{sub 2}O {equivalent_to} 0.251--1.815 mol/kg-H{sub 2}O) were measured over the temperature range 25 to 75 C at saturation vapor pressures in glass cells with parallel platinum electrodes. Sixteen series of measurements were made involving three samples of boric acid from different sources. Conductance measurements were also made at 15.5 and 30.5 g/kg-H{sub 2}O over the temperature range 100 to 350 C at 50 C intervals with a metallic cell fitted with concentric platinum electrodes. The specific conductances of H{sub 3}BO{sub 3} (aq)were calculated after correction for the conductance of the solvent (water) and are tabulated in this report. At the specific conditions requested in the project description, namely a concentration of 110 g/kg-H{sub 2}O and 65 C, the specific conductance of boric acid is 293.2 {+-} 1.8 microSiemens/cm based on duplicate measurements of four independent solutions. The results from these tests will be utilized by the Tokamak Physics Experimental Project (TPX).

  5. Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

    NASA Technical Reports Server (NTRS)

    Tolbert, Margaret A.; Rossi, Michel J.; Golden, David M.

    1988-01-01

    The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

  6. Delayed production of sulfuric acid condensation nuclei in the polar stratosphere from El Chichon volcanic vapors

    NASA Technical Reports Server (NTRS)

    Hofmann, D. J.; Rosen, J. M.; Gringel, W.

    1985-01-01

    It is pointed out that measurements of the vertical profiles of atmospheric condensation nuclei (CN) have been conducted since 1973. Studies with a new instrument revealed that the CN concentration undergoes a remarkable annual variation in the 30-km region characterized by a large increase in the late winter/early spring period with a subsequent decay during the remainder of the year. The event particles are observed to be volatile at 150 C, suggesting a sulfuric acid-water composition similar to that found in the normal 20 km aerosol layer. The development of about 10 to the 7th metric tons of sulfuric acid aerosol following the injection of sulfurous gases by El Chichon in April 1982, prompted Hofmann and Rosen (1983) to predict a very large CN event for 1983. The present investigation is concerned with the actual observation of the predicted event. Attention is given to the observation of a very large increase of what appear to be small sulfuric acid droplets at 30-km altitude in January 1983 over Laramie, WY, in January 1983.

  7. The effect of acids on fluorescence of coumarin-6 in organic solvents

    NASA Astrophysics Data System (ADS)

    Mina, M. V.; Puzyk, I. P.; Puzyk, M. V.

    2013-02-01

    The effect of acids (HCl, HClO4, HNO3, and CH3COOH) on the fluorescence of coumarin-6 in organic solvents (acetonitrile, acetone, butanol-1, and ethanol) is studied. The regions of acid (HCl, HClO4, HNO3) concentrations that lead to a change in the fluorescence spectra are determined for each of the solvents. It is shown that, for all the solvents studied, acetic acid with a concentration within the region 10-1-10-6 M causes no significant changes in the fluorescence spectrum of coumarin-6. A mechanism of the coumarin-6 protonation is proposed.

  8. Vapor sensing mechanism of acid on copper phthalocyanine thin films studied by electrical conductivity

    NASA Astrophysics Data System (ADS)

    Singh, Sukhwinder; Saini, G. S. S.; Tripathi, S. K.

    2013-06-01

    The electrical conductivity of thin films of iron phthalocyanine on glass substrates by thermal evaporation technique have been investigated. The electrical conductivity of thin films of these complexes changes when exposed to oxidizing and reducing gases such as halogens, ammonia, water and NOX. Thermal activation energy in the intrinsic region and impurity scattering region can be calculated by using Arrhenius plot. The dark conductivity and photoconductivity have been taken at different temperatures in the range 312-389 K. These films have been studied as chemical sensors for dilute sulphuric acid.

  9. Laboratory measurements of the microwave opacity and vapor pressure of sulfuric acid vapor under simulated conditions for the middle atmosphere of Venus

    NASA Technical Reports Server (NTRS)

    Steffes, P. G.

    1985-01-01

    Microwave absorption measurements at wavelengths of 13.4 and 3.6 cm were made in gaseous H2SO4 in a CO2 atmosphere under simulated conditions for the Venus middle atmosphere. The results suggest that abundances of gaseous H2SO4 on the order of 15-30 ppm could account for the absorption observed by radio occultation measurements at these wavelengths. They also imply that such abundances would correspond to saturation vapor pressure existing at or above the 46-48-km range, which correlates with the observed cloud base.

  10. Improvement in electrochemical capacitance of activated carbon from scrap tires by nitric acid treatment

    NASA Astrophysics Data System (ADS)

    Han, Yan; Zhao, Ping-Ping; Dong, Xiao-Ting; Zhang, Cui; Liu, Shuang-Xi

    2014-12-01

    Activated carbon (AC) obtained from the industrial pyrolytic tire char is treated by concentrated nitric acid (AC-HNO3) and then used as the electrode material for supercapacitors. Surface properties and electrochemical capacitances of AC and ACHNO3 are studied. It is found that the morphology and the porous texture for AC and AC-HNO3 have little difference, while the oxygen content increases and functional groups change after the acid treatment. Electrochemical results demonstrate that the AC-HNO3 electrode displays higher specific capacitance, better stability and cycling performance, and lower equivalent series resistance, indicating that AC obtained from the industrial pyrolytic tire char treated by concentrated nitric acid is applicable for supercapacitors.

  11. Nitric acid and ammonia emissions from a mid-latitude prescribed wetlands fire

    NASA Astrophysics Data System (ADS)

    LeBel, P. J.; Cofer, W. R., III; Levine, J. S.; Vay, S. A.; Roberts, P. D.

    1988-08-01

    We have obtained the first simultaneous measurements of gaseous nitric acid (HNO3) and ammonia (NH3) in the smoke plume of a wetlands biomass burn. These measurements were made using tungsten oxide-coated diffusion denuder tubes from a helicopter during a prescribed burn at the Merritt Island National Wildlife Refuge, located at the NASA John F. Kennedy Space Center, Florida, on November 9, 1987. The mean NH3 and HNO3 mixing ratios measured in the smoke plume were 19 ppbv and 14 ppbv, respectively, both significantly higher than background mixing ratios. Nitric acid correlated well with carbon dioxide (CO2) produced by the combustion. The mean CO2-normalized emission ratio for HNO3 was found to be 1.2 × 10-4. Ammonia, however, did not correlate well with CO2 suggesting a more complex relationship between combustion and production/release of NH3.

  12. Vapor Intrusion

    EPA Pesticide Factsheets

    Vapor intrusion occurs when there is a migration of volatile chemicals from contaminated groundwater or soil into an overlying building. Volatile chemicals can emit vapors that may migrate through subsurface soils and into indoor air spaces.

  13. Determination of inorganic and total mercury by vapor generation atomic absorption spectrometry using different temperatures of the measurement cell

    NASA Astrophysics Data System (ADS)

    Kaercher, Luiz Eduardo; Goldschmidt, Fabiane; Paniz, José Neri Gottfried; de Moraes Flores, Érico Marlon; Dressler, Valderi Luiz

    2005-06-01

    A simple and inexpensive laboratory-built flow injection vapor generation system coupled to atomic absorption spectrometry (FI-VG AAS) for inorganic and total mercury determination has been developed. It is based on the vapor generation of total mercury and a selective detection of Hg 2 + or total mercury by varying the temperature of the measurement cell. Only the inorganic mercury is measured when the quartz cell is at room temperature, and when the cell is heated to 650 °C or higher the total Hg concentration is measured. The organic Hg concentration in the sample is calculated from the difference between the total Hg and Hg 2 + concentrations. Parameters such as the type of acid (HCl or HNO 3) and its concentration, reductant (NaBH 4) concentration, carrier solution (HCl) flow rate, carrier gas flow rate, sample volume and quartz cell temperature, which influence FI-VG AAS system performance, were systematically investigated. The optimized conditions for Hg 2 + and total Hg determinations were: 1.0 mol l - 1 HCl as carrier solution, carrier flow rate of 3.5 ml min - 1 , 0.1% (m/v) NaBH 4, reductant flow rate of 1.0 ml min - 1 and carrier gas flow rate of 200 ml min - 1 . The relative standard deviation (RSD) is lower than 5.0% for a 1.0 μg l - 1 Hg solution and the limit of quantification (LOQ, 10 s) is 55 ng g - 1 . Certified samples of dogfish muscle (DORM-1 and DORM-2) and non-certified fish samples were analyzed, using a 6.0 mol l - 1 HCl solution for analyte extraction. The Hg 2 + and CH 3Hg + concentrations found were in agreement with certified ones.

  14. Calibration and evaluation of nitric acid and ammonia permeation tubes by UV optical absorption.

    PubMed

    Neuman, J Andrew; Ryerson, Thomas B; Huey, L Gregory; Jakoubek, Roger; Nowak, John B; Simons, Craig; Fehsenfeld, Frederick C

    2003-07-01

    An ultraviolet (UV) optical absorption system has been developed for absolute calibrations of nitric acid (HNO3) and ammonia (NH3) permeation tube emission rates. Using this technique, dilute mixtures containing NH3 or HNO3, both of which interact strongly with many surfaces, are accurately measured at levels below a part per million by volume. This compact and portable instrument operates continuously and autonomously to rapidly (<1 h) quantify the emission of trace gases from permeation devices that are commonly used to calibrate air-monitoring instruments. The output from several HNO3 and NH3 permeation tubes, with emission rates that ranged between 13 and 150 ng/min, was examined as a function of temperature, pressure, and carrier gas flow. Absorptions of 0.015% can be detected which allows a precision (3sigma) of +/-1 ng/min for the HNO3 and NH3 permeation tubes studied here. The accuracy of the measurements, which relies on published UV absorption cross sections, is estimated to be +/-10%. Measurements of permeation tube emission rates using ion chromatography analysis are made to further assess measurement accuracy. The output from the HNO3 and NH3 permeation tubes examined here was stable over the study period, which ranged between 3 months and 1 year for each permeation tube.

  15. Direct Real-Time Detection of Vapors from Explosive Compounds

    SciTech Connect

    Ewing, Robert G.; Clowers, Brian H.; Atkinson, David A.

    2013-10-03

    The real-time detection of vapors from low volatility explosives including PETN, tetryl, RDX and nitroglycerine along with various compositions containing these substances is demonstrated. This was accomplished with an atmospheric flow tube (AFT) using a non-radioactive ionization source and coupled to a mass spectrometer. Direct vapor detection was demonstrated in less than 5 seconds at ambient temperature without sample pre-concentration. The several seconds of residence time of analytes in the AFT provides a significant opportunity for reactant ions to interact with analyte vapors to achieve ionization. This extended reaction time, combined with the selective ionization using the nitrate reactant ions (NO3- and NO3-•HNO3), enables highly sensitive explosives detection. Observed signals from diluted explosive vapors indicate detection limits below 10 ppqv using selected ion monitoring (SIM) of the explosive-nitrate adduct at m/z 349, 378, 284 and 289 for tetryl, PETN, RDX and NG respectively. Also provided is a demonstration of the vapor detection from 10 different energetic formulations, including double base propellants, plastic explosives and commercial blasting explosives using SIM for the NG, PETN and RDX product ions.

  16. Reversible resistance modulation in mesoscopic silver wires induced by exposure to amine vapor.

    PubMed

    Murray, B J; Newberg, J T; Walter, E C; Li, Q; Hemminger, J C; Penner, R M

    2005-08-15

    Ensembles of silver nanowires (AgNEs) with diameters ranging from 200 nm to 1.0 microm have been prepared by electrochemical step edge decoration. These AgNEs showed a rapid (< 5 s), reversible increase in resistance upon exposure to the vapor of ammonia, trimethylamine, and pyridine. The amplitude of the resistance change was up to +3000% (DeltaR/Ro)-more than 2 orders of magnitude larger than can be explained based on boundary layer scattering effects. We experimentally probe the mechanism for this resistance modulation in the case of ammonia, and we propose a model to describe it. Conductive tip atomic force microscopy was used to probe individual sections of nanowires in AgNEs; these data revealed that the resistance change caused by NH(3) exposure was concentrated within a minority (approximately 10%) of the 5-microm wire segments that were probed--not uniformly distributed along each nanowire. All AgNEs showed a temperature dependence of their resistance, alpha, that was smaller than expected for silver metal. Highly sensitive AgNEs sometimes showed a negative alpha, characteristic of semiconductors, but negative alpha values were never observed for AgNEs with a low sensitivity to NH3. AgNEs did not respond to hydrocarbons, O2, H2O, N2, CO, or Ar, but a large (DeltaR/Ro > |-50%|) irreversible decrease in resistance was seen upon exposures to acids including HCl, HNO3, and H2SO4. Based on these and other data, we propose a model in which oxidized constrictions in silver nanowires limit the conductivity of the wire and provide a means for "gating" conduction based on the protonation state of the oxide surface.

  17. Recycling of metal-organic chemical vapor deposition waste of GaN based power device and LED industry by acidic leaching: Process optimization and kinetics study

    NASA Astrophysics Data System (ADS)

    Swain, Basudev; Mishra, Chinmayee; Kang, Leeseung; Park, Kyung-Soo; Lee, Chan Gi; Hong, Hyun Seon; Park, Jeung-Jin

    2015-05-01

    Recovery of metal values from GaN, a metal-organic chemical vapor deposition (MOCVD) waste of GaN based power device and LED industry is investigated by acidic leaching. Leaching kinetics of gallium rich MOCVD waste is studied and the process is optimized. The gallium rich waste MOCVD dust is characterized by XRD and ICP-AES analysis followed by aqua regia digestion. Different mineral acids are used to find out the best lixiviant for selective leaching of the gallium and indium. Concentrated HCl is relatively better lixiviant having reasonably faster kinetic and better leaching efficiency. Various leaching process parameters like effect of acidity, pulp density, temperature and concentration of catalyst on the leaching efficiency of gallium and indium are investigated. Reasonably, 4 M HCl, a pulp density of 50 g/L, 100 °C and stirring rate of 400 rpm are the effective optimum condition for quantitative leaching of gallium and indium.

  18. Sorption of vapors of some organic liquids on soil humic acid and its relation to partitioning of organic compounds in soil organic matter

    USGS Publications Warehouse

    Chlou, G.T.; Kile, D.E.; Malcolm, R.L.

    1988-01-01

    Vapor sorption of water, ethanol, benzene, hexane, carbon tetrachloride, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene, and 1,2-dibromoethane on (Sanhedron) soil humic acid has been determined at room temperature. Isotherms for all organic liquids are highly linear over a wide range of relative pressure (P/P??), characteristic of the partitioning (dissolution) of the organic compounds in soil humic acid. Polar liquids exhibit markedly greater sorption capacities on soil humic acid than relatively nonpolar liquids, in keeping with the polar nature of the soil humic acid as a partition medium. The limiting sorption (partition) capacities of relatively non-polar liquids are remarkably similar when expressed in terms of volumes per unit weight of soil humic acid. The soil humic acid is found to be about half as effective as soil organic matter in sorption of relatively nonpolar organic compounds. The nearly constant limiting sorption capacity for nonpolar organic liquids with soil humic acid on a volume-to-weight basis and its efficiency in sorption relative to soil organic matter provide a basis for predicting the approximate sorption (partition) coefficients of similar compounds in uptake by soil in aqueous systems.

  19. Influence of hydrofluoric acid on extraction of thorium using a commercially available extraction chromatographic resin.

    PubMed

    Shimada-Fujiwara, Asako; Hoshi, Akiko; Kameo, Yutaka; Nakashima, Mikio

    2009-05-01

    The dependence of Th recovery on hydrofluoric acid (HF) concentration in nitric acid (HNO(3)) solutions (1-5 mol/dm(3)) containing 1x10(-6) mol/dm(3) of Th and various concentrations of HF and the elution behavior were studied using a commercially available UTEVA (for uranium and tetravalent actinide) resin column. Thorium recovery decreased with an increase in HF concentration in the sample solutions. The concentration of HF at which Th recovery started to decrease was approximately 1x10(-4) mol/dm(3) in 1 mol/dm(3) HNO(3) solution, approximately 1x10(-3) mol/dm(3) in 3 mol/dm(3) HNO(3) solution, and approximately 1x10(-2) mol/dm(3) in 5 mol/dm(3) HNO(3) solution. When Al(NO(3))(3) (0.2 mol/dm(3)) or Fe(NO(3))(3) (0.6 mol/dm(3)) was added as a masking agent for F(-) to the Th solution containing 1x10(-1) mol/dm(3) HF and 1 mol/dm(3) HNO(3), Th recovery improved from 1.4+/-0.3% to 95+/-5% or 93+/-3%. Effective extraction of Th using UTEVA resin was achieved by selecting the concentration of HNO(3) and/or adding masking agents such as Al(NO(3))(3) according to the concentration of HF in the sample solution.

  20. Extraction of rare earth oxides using supercritical carbon dioxide modified with Tri-n-butyl phosphate–nitric acid adducts

    DOE PAGES

    Baek, Donna L.; Fox, Robert V.; Case, Mary E.; ...

    2016-06-14

    A new tri-n-butylphosphate–nitric acid (TBP–HNO3) adduct was prepared by combining TBP and fuming (90%) HNO3. The adduct was characterized, and its phase-equilibrium behavior in supercritical carbon dioxide is reported. Supercritical carbon dioxide (sc-CO2) was modified with this new adduct [TBP(HNO3)5.2(H2O)1.7], and the extraction efficacies of selected rare earth oxides (Y, Ce, Eu, Tb, and Dy) at 338 K and 34.5 MPa were compared with those obtained using an adduct formed from concentrated (70%) HNO3 and TBP [TBP(HNO3)1.7(H2O)0.6]. All rare earth oxides tested with both adduct species could be extracted with the exception of cerium oxide. Furthermore, the water and acidmore » concentrations in the different adducts were found to play a significant role in rare earth oxide extraction efficiency.« less

  1. The influence of tributyl phosphate on molybdenum extraction with solutions of dibutyl phosphoric acid

    NASA Astrophysics Data System (ADS)

    Goletskiy, N. D.; Zilberman, B. Ya.; Fedorov, Yu. S.; Khonina, I. V.; Kukharev, D. N.

    2006-01-01

    Comparative investigations were carried out to study the influence of TBP on Mo extraction by HDBP solutions in xylene and TBP in xylene. The dependences of DMo on HNO3 concentration for both HDBP and D2EHPA have minima at about 3 mol/L HNO3. This shows similar extraction properties of HDBP and D2EHPA. The presence of TBP in the solvent results in the reduction of Mo extraction and in an increase in the formal slopes of the falling and rising parts of the logDMo — log[HNO3] curve from -0.5 and +2 up to -2 and +4. Solvent loading curves with Mo show that in the absence of TBP a molybdenum solvate with two molecules of HDBP is formed at low acidity. Anomalous increase in the maximum solvent loading in the presence of TBP is caused by the ability of TBP to extract Mo from oversaturated low acidity solutions following the acidic mechanism. A molybdenum solvate with two HDBP molecules and one HNO3 molecule is possibly formed at high acidity. A flowsheet for Mo recovery from HLW with HDBP-TBP solvent was tested in centrifugal contactors.

  2. Polymorph-dependent titanium dioxide nanoparticle dissolution in acidic and alkali digestions

    EPA Science Inventory

    Multiple polymorphs (anatase, brookite and rutile) of titanium dioxide nanoparticles (TiO2-NPs) with variable structures were quantified in environmental matrices via microwave-based hydrofluoric (HF) and nitric (HNO3) mixed acid digestion and muffle furnace (MF)-based potassium ...

  3. Carbon Dioxide and Water Vapor Exchange in the Crassulacean Acid Metabolism Plant Kalanchoë pinnáta during a Prolonged Light Period

    PubMed Central

    Winter, Klaus

    1980-01-01

    Net CO2 and water vapor exchange were studied in the Crassulacean acid metabolism plant Kalanchoë pinnáta during a normal 12-hour light/12-hour dark cycle and during a prolonged light period. Leaf temperature and leaf-air vapor pressure difference were kept constant at 20 C and 9 to 10 millibar. There was a 25% increase in the rate of CO2 fixation during the first 6 hours prolonged light without change in stomatal conductance. This was associated with a decrease in the intracellular partial pressure of CO2, a decrease in the stimulation of net CO2 uptake by 2% O2, and a decrease in the CO2 compensation point from 45 to 0 microbar. In the normal light period after deacidification, leaves showed a normal light dependence of CO2 uptake but, in prolonged light, CO2 uptake was scarcely light-dependent. The increase in titratable acidity in prolonged light was similar to that in the dark. The results suggest a change from C3 photosynthetic CO2 fixation in the second part of the 12-hour light period to a mixed metabolism in prolonged light with both ribulose bisphosphate carboxylase and phosphoenolpyruvate carboxylase as primary carboxylating enzymes. PMID:16661552

  4. Advanced zirconia-coated carbonyl-iron particles for acidic magnetorheological finishing of chemical-vapor-deposited ZnS and other IR materials

    NASA Astrophysics Data System (ADS)

    Salzman, S.; Giannechini, L. J.; Romanofsky, H. J.; Golini, N.; Taylor, B.; Jacobs, S. D.; Lambropoulos, J. C.

    2015-10-01

    We present a modified version of zirconia-coated carbonyl-iron (CI) particles that were invented at the University of Rochester in 2008. The amount of zirconia on the coating is increased to further protect the iron particles from corrosion when introduced to an acidic environment. Five low-pH, magnetorheological (MR) fluids were made with five acids: acetic, hydrochloric, nitric, phosphoric, and hydrofluoric. All fluids were based on the modified zirconia-coated CI particles. Off-line viscosity and pH stability were measured for all acidic MR fluids to determine the ideal fluid composition for acidic MR finishing of chemical-vapor-deposited (CVD) zinc sulfide (ZnS) and other infrared (IR) optical materials, such as hot-isostatic-pressed (HIP) ZnS, CVD zinc selenide (ZnSe), and magnesium fluoride (MgF2). Results show significant reduction in surface artifacts (millimeter-size, pebble-like structures on the finished surface) for several standard-grade CVD ZnS substrates and good surface roughness for the non-CVD MgF2 substrate when MR finished with our advanced acidic MR fluid.

  5. Oxidative degradation of bis (2,4,4-trimethylpentyl) dithiophosphinic acid in nitric acid studied by electrospray ionization mass spectrometry

    SciTech Connect

    G. S. Groenewold; D. R. Peterman

    2012-10-01

    Samples of bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex-301) were analyzed using direct infusion electrospray ionization mass spectrometry. Positive ion spectra of standard and stereo-pure acids displayed ions typical of the unmodified compound, cationized monomeric and dimeric cluster ion species. In addition, a significant ions 2 u less than the dimeric clusters were seen, that correspond to an oxidatively coupled species designated Cyx2 that is observed as H- or Na-cationized species in the electrospray analyses. Based on uncorrected ion intensities, Cyx2 is estimated to account for about 20% of the total in the standard materials. When samples that were contacted with 3 M HNO3 were analyzed, the positive ion spectrum consisted nearly entirely of ions derived from the oxidatively coupled product, indicating that the acid promotes coupling. The negative ion spectra of the standard acids consisted nearly entirely of the conjugate base that is formed by deprotonation of the acids, and cluster ions containing multiple acid molecules. The negative spectra of the HNO3-contacted samples also contained the conjugate base of the unmodified acid, but also two other species that correspond to the dioxo- and perthio- derivatives. It is concluded that HNO3 contact causes significant oxidation, forming at least three major products, Cyx2, the perthio-acid, and the dioxo-acid.

  6. Tuning the acid/metal balance of carbon nanofiber-supported nickel catalysts for hydrolytic hydrogenation of cellulose.

    PubMed

    Van de Vyver, Stijn; Geboers, Jan; Schutyser, Wouter; Dusselier, Michiel; Eloy, Pierre; Dornez, Emmie; Seo, Jin Won; Courtin, Christophe M; Gaigneaux, Eric M; Jacobs, Pierre A; Sels, Bert F

    2012-08-01

    Carbon nanofibers (CNFs) are a class of graphitic support materials with considerable potential for catalytic conversion of biomass. Earlier, we demonstrated the hydrolytic hydrogenation of cellulose over reshaped nickel particles attached at the tip of CNFs. The aim of this follow-up study was to find a relationship between the acid/metal balance of the Ni/CNFs and their performance in the catalytic conversion of cellulose. After oxidation and incipient wetness impregnation with Ni, the Ni/CNFs were characterized by various analytical methods. To prepare a selective Ni/CNF catalyst, the influences of the nature of oxidation agent, Ni activation, and Ni loading were investigated. Under the applied reaction conditions, the best result, that is, 76 % yield in hexitols with 69 % sorbitol selectivity at 93 % conversion of cellulose, was obtained on a 7.5 wt % Ni/CNF catalyst prepared by chemical vapor deposition of CH(4) on a Ni/γ-Al(2)O(3) catalyst, followed by oxidation in HNO(3) (twice for 1 h at 383 K), incipient wetness impregnation, and reduction at 773 K under H(2). This preparation method leads to a properly balanced Ni/CNF catalyst in terms of Ni dispersion and hydrogenation capacity on the one hand, and the number of acidic surface-oxygen groups responsible for the acid-catalyzed hydrolysis on the other.

  7. Vapor Bubbles

    NASA Astrophysics Data System (ADS)

    Prosperetti, Andrea

    2017-01-01

    This article reviews the fundamental physics of vapor bubbles in liquids. Work on bubble growth and condensation for stationary and translating bubbles is summarized and the differences with bubbles containing a permanent gas stressed. In particular, it is shown that the natural frequency of a vapor bubble is proportional not to the inverse radius, as for a gas bubble, but to the inverse radius raised to the power 2/3. Permanent gas dissolved in the liquid diffuses into the bubble with strong effects on its dynamics. The effects of the diffusion of heat and mass on the propagation of pressure waves in a vaporous bubbly liquid are discussed. Other topics briefly touched on include thermocapillary flow, plasmonic nanobubbles, and vapor bubbles in an immiscible liquid.

  8. Stratospheric aerosol acidity, density, and refractive index deduced from SAGE 2 and NMC temperature data

    NASA Technical Reports Server (NTRS)

    Yue, G. K.; Poole, L. R.; Wang, P.-H.; Chiou, E. W.

    1994-01-01

    Water vapor concentrations obtained by the Stratospheric Aerosol and Gas Experiment 2 (SAGE 2) and collocated temperatures provided by the National Meteorological Center (NMC) from 1986 to 1990 are used to deduce seasonally and zonally averaged acidity, density, and refractive index of stratospheric aerosols. It is found that the weight percentage of sulfuric acid in the aerosols increases from about 60 just above the tropopause to about 86 at 35 km. The density increases from about 1.55 to 1.85 g/cu cm between the same altitude limits. Some seasonal variations of composition and density are evident at high latitudes. The refractive indices at 1.02, 0.694, and 0.532 micrometers increase, respectively, from about 1.425, 1.430, and 1.435 just above the tropopause to about 1.445, 1.455, and 1.458 at altitudes above 27 km, depending on the season and latitude. The aerosol properties presented can be used in models to study the effectiveness of heterogeneous chemistry, the mass loading of stratospheric aerosols, and the extinction and backscatter of aerosols at different wavelengths. Computed aerosol surface areas, rate coefficients for the heterogeneous reaction ClONO2 + H2O yields HOCl + HNO3 and aerosol mass concentrations before and after the Pinatubo eruption in June 1991 are shown as sample applications.

  9. Electrolyte vapor condenser

    DOEpatents

    Sederquist, R.A.; Szydlowski, D.F.; Sawyer, R.D.

    1983-02-08

    A system is disclosed for removing electrolyte from a fuel cell gas stream. The gas stream containing electrolyte vapor is supercooled utilizing conventional heat exchangers and the thus supercooled gas stream is passed over high surface area passive condensers. The condensed electrolyte is then drained from the condenser and the remainder of the gas stream passed on. The system is particularly useful for electrolytes such as phosphoric acid and molten carbonate, but can be used for other electrolyte cells and simple vapor separation as well. 3 figs.

  10. Field test of four methods for gas-phase ambient nitric acid

    NASA Astrophysics Data System (ADS)

    Arnold, J. R.; Hartsell, Benjamin E.; Luke, Winston T.; Rahmat Ullah, S. M.; Dasgupta, Purnendu K.; Greg Huey, L.; Tate, Paul

    Three semi-continuous methods for detecting nitric acid (HNO 3) were tested against the annular denuder + filter pack (ADS) integrated collection technique at the Tampa Bay Regional Atmospheric Chemistry Experiment (BRACE) Sydney research station ˜20km downwind of the Tampa, Florida, urban core. The semi-continuous instruments included: two slightly differing implementations of the NOY-NO (total oxides of nitrogen minus that total denuded of HNO 3) denuder difference technique, one from the NOAA Air Resources Lab (ARL), and one from Atmospheric Research and Analysis, Inc. (ARA); the parallel plate wet diffusion scrubber + online ion chromatography technique from Texas Tech University (TTU); and the chemical ionization mass spectrometer from the Georgia Institute of Technology (GIT). Twelve hour ADS samples were collected by the University of South Florida (USF). Results for 10 min samples computed from the various higher sampling frequencies of each semi-continuous instrument showed good agreement (R2>0.7) for afternoon periods of the highest production and accumulation of HNO 3. Further, agreement was within ±30% for these instruments even at HNO 3 concentrations <0.30ppb. The USF ADS results were biased low, however, by 44%, on average, compared to the corporate 12 h aggregated means from the semi-continuous methods, and by >60% for the nighttime samples; ADS results were below the corporate mean maximum HNO 3 concentration by >30% as well. The four instruments using semi-continuous methods, by contrast, were all within 10% of each other's 12 h mean mixing ratios. While only ARA employed a formal minimum detection limit at 0.050 ppb, error analysis with the other techniques established that at the same level of precision, TTU's effective limit was approximately the same as ARA's and that ARL's limit was 0.030 ppb; analysis for GIT showed no apparent effective limit at the levels of HNO 3 encountered in this field study. The importance of sample inlet height for

  11. The Effect of Incorporation of HNO(sub 3) Into Liquid Sulfuric Acid on Heterogeneous Reaction Probabilities

    NASA Technical Reports Server (NTRS)

    Zhang, R.; Leu, M-T.; Keyser, L.

    1994-01-01

    Using a fast-flow reactor coupled to a quadrupole mass spectrometer, the heterogeneous reactions of C1ONO2 + HCl and HOCl + HCl as well as hydrolysis of N2O5 and C1ONO2 were investigated on liquid sulfuric acid, with particular emphasis on the effect of incorporation of HNO3 on the reaction probabilities.

  12. Reactions Between Water Soluble Organic Acids and Nitrates in Atmospheric Aerosols: Recycling of Nitric Acid and Formation of Organic Salts

    SciTech Connect

    Wang, Bingbing; Laskin, Alexander

    2014-03-25

    Atmospheric particles often include a complex mixture of nitrate and secondary organic materials accumulated within the same individual particles. Nitrate as an important inorganic component can be chemically formed in the atmosphere. For instance, formation of sodium nitrate (NaNO3) and calcium nitrate Ca(NO3)2 when nitrogen oxide and nitric acid (HNO3) species react with sea salt and calcite, respectively. Organic acids contribute a significant fraction of photochemically formed secondary organics that can condense on the preexisting nitrate-containing particles. Here, we present a systematic microanalysis study on chemical composition of laboratory generated particles composed of water soluble organic acids and nitrates (i.e. NaNO3 and Ca(NO3)2) investigated using computer controlled scanning electron microscopy with energy dispersive analysis of X-rays (CCSEM/EDX) and Fourier transform infrared micro-spectroscopy (micro-FTIR). The results show that water-soluble organic acids can react with nitrates releasing gaseous HNO3 during dehydration process. These reactions are attributed to acid displacement of nitrate with weak organic acids driven by the evaporation of HNO3 into gas phase due to its relatively high volatility. The reactions result in significant nitrate depletion and formation of organic salts in mixed organic acids/nitrate particles that in turn may affect their physical and chemical properties relevant to atmospheric environment and climate. Airborne nitrate concentrations are estimated by thermodynamic calculations corresponding to various nitrate depletions in selected organic acids of atmospheric relevance. The results indicate a potential mechanism of HNO3 recycling, which may further affect concentrations of gas- and aerosol-phase species in the atmosphere and the heterogeneous reaction chemistry between them.

  13. Application of Lactobacillus immobilized by Activated Carbon Fiber in Fermentation of Lactic Acid in Starch Wastewater

    NASA Astrophysics Data System (ADS)

    Xu, Wei; Wang, Peng; Chi, Guoda; Huang, Chenyong

    2010-11-01

    Activated carbon fibers (ACF) as the carrier of Lactobacillus was introduced into fermenting system, and a method of modifying the surface of ACF by HNO3-Fe (III) was established. Factors that affect ACF carrier's effect on immobilization of Lactobacillus were studied. HCl, H2SO4, HNO3 and FeCl3 solutions were respectively used to modify the surface properties of ACF. The amount of Fe (III) carried on ACF surface was 0.1563 mol/kg after ACF surface was modified by HNO3 for 5 h and then by 0.1 mol/L FeCl3 for 4 h, when the thickness of Lactobacillus on a single silk of carrier reached 40 μm. When ACF modified by HNO3-Fe (III) was applied in the fermentation of lactic acid in starch industry wastewater, the fermentation period reduced by 8 h and the output of L-lactic acid was 65.5 g/L, which was 3.3% more than that fermented without the carrier.

  14. Shape-Persistent, Thermoresponsive Polypeptide Brushes Prepared by Vapor Deposition Surface-Initiated Ring-Opening Polymerization of α-Amino Acid N -Carboxyanhydrides

    DOE PAGES

    Shen, Yong; Desseaux, Solenne; Aden, Bethany; ...

    2015-04-20

    We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

  15. Shape-Persistent, Thermoresponsive Polypeptide Brushes Prepared by Vapor Deposition Surface-Initiated Ring-Opening Polymerization of α-Amino Acid N -Carboxyanhydrides

    SciTech Connect

    Shen, Yong; Desseaux, Solenne; Aden, Bethany; Lokitz, Bradley S.; Kilbey, S. Michael; Li, Zhibo; Klok, Harm-Anton

    2015-04-20

    We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modified L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.

  16. Chemical Degradation Studies on a Series of Dithiophosphinic Acids

    SciTech Connect

    Melissa E. Freiderich; Dean R. Peterman; John R. Klaehn; Philippe Marc; Laetitia H. Delmau

    2014-04-01

    A significant increase in the stability of a series of dithiophosphinic acids (DPAHs) under oxidizing acidic conditions was achieved. The degradation behavior of a series of DPAHs, designed for lanthanide/actinide separation, was examined. The stability of the DPAHs, when contacted with varying nitric acid concentrations, was tested and monitored using 31P {1H} NMR. Changes in the functional groups of the DPAHs resulted in substantial increases in the stability. However, when placed in contact with 2 M HNO3 all the DPAHs eventually showed signs of degradation. The addition of a radical scavenger, hydrazine, inhibited the degradation of the DPAHs. In the presence of a small concentration of hydrazine, five of the DPAHs remained stable for over a month in direct contact with 2 M HNO3.

  17. Chemical Degradation Studies on a Series of Dithiophosphinic Acids

    SciTech Connect

    Freiderich, Melissa E; Delmau, Laetitia Helene; Peterman, D. R.; Marc, Philippe L; Klaehn, John D.

    2014-01-01

    In this study a significant increase in the stability of a series of dithiophosphinic acids (DPAHs) under oxidizing acidic conditions was achieved. The degradation behavior of a series of DPAHs, designed for lanthanide/actinide separation, was examined. The stability of the DPAHs, when contacted with varying nitric acid concentrations, was tested and monitored using 31P {1H} NMR. Changes in the functional groups of the DPAHs resulted in substantial increases in the stability. However, all the DPAHs eventually showed signs of degradation when placed in contact with 2 M HNO3. The addition of a radical scavenger, hydrazine, inhibited the degradation of the DPAHs. With small amounts of hydrazine, five of the DPAHs remained stable for over a month in direct contact with 2 M HNO3.

  18. Water, sulfur dioxide and nitric acid adsorption on calcium carbonate: a transmission and ATR-FTIR study.

    PubMed

    Al-Hosney, H A; Grassian, V H

    2005-03-21

    Calcium carbonate (CaCO3) is a reactive component of mineral dust aerosol as well as buildings, statues and monuments. In this study, attenuated total reflection (ATR) and transmission Fourier transform infrared spectroscopy (FTIR) have been used to study the uptake of water, sulfur dioxide and nitric acid on CaCO3 particles at 296 K. Under atmospheric conditions, CaCO3 particles are terminated by a Ca(OH)(CO3H) surface layer. In the presence of water vapor between 5 and 95% relative humidity (RH), water molecularly adsorbs on the Ca(OH)(CO3H) surface resulting in the formation of an adsorbed thin water film. The adsorbed water film assists in the enhanced uptake of sulfur dioxide and nitric acid on CaCO3 in several ways. Under dry conditions (near 0% RH), sulfur dioxide and nitric acid react with the Ca(OH)(CO3H) surface to form adsorbed carbonic acid (H2CO3) along with sulfite and nitrate, respectively. Adsorbed carbonic acid is stable on the surface under vacuum conditions. Once the surface saturates with a carbonic acid capping layer, there is no additional uptake of gas-phase sulfur dioxide and nitric acid. However, upon adsorption of water, carbonic acid dissociates to form gaseous carbon dioxide and there is further uptake of sulfur dioxide and nitric acid. In addition, adsorbed water increases the mobility of the ions at the surface and enhances uptake of SO2 and HNO3. In the presence of adsorbed water, CaSO3 forms islands of a crystalline hydrate whereas Ca(NO3)2 forms a deliquescent layer or micropuddles. Thus adsorbed water plays an important and multi-faceted role in the uptake of pollutant gases on CaCO3.

  19. Dispersibility of vapor phase oxygen and nitrogen functionalized multi-walled carbon nanotubes in various organic solvents

    PubMed Central

    Khazaee, Maryam; Xia, Wei; Lackner, Gerhard; Mendes, Rafael G.; Rümmeli, Mark; Muhler, Martin; Lupascu, Doru C.

    2016-01-01

    The synthesis and characterization of gas phase oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (OMWCNTs and NMWCNTs) and the dispersibility of these tubes in organic solvents were investigated. Recently, carbon nanotubes have shown supreme capacity to effectively enhance the efficiency of organic solar cells (OSCs). A critical challenge is to individualize tubes from their bundles in order to provide homogenous nano-domains in the active layer of OSCs. OMWCNTs and NMWCNTs were synthesized via HNO3 vapor and NH3 treatments, respectively. Surface functional groups and the structure of the tubes were analyzed by temperature-programmed desorption, Fourier transform infrared spectroscopy, transmission electron microscopy, and Raman spectroscopy which confirmed the formation of functional groups on the tube surface and the enhancement of surface defects. Elemental analysis demonstrated that the oxygen and nitrogen content increased with increasing treatment time of the multi-walled carbon nanotube (MWCNT) in HNO3 vapor. According to ultra-violet visible spectroscopy, modification of the MWCNT increased the extinction coefficients of the tubes owing to enhanced compatibility of the functionalized tubes with organic matrices. PMID:27188622

  20. Thermal decomposition of gaseous ammonium nitrate at low pressure: kinetic modeling of product formation and heterogeneous decomposition of nitric acid.

    PubMed

    Park, J; Lin, M C

    2009-12-03

    The thermal decomposition of ammonium nitrate, NH(4)NO(3) (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH(4)NO(3) at 423 K was proposed to produce equal amounts of NH(3) and HNO(3), followed by the decomposition reaction of HNO(3), HNO(3) + M --> OH + NO(2) + M (where M = third-body and reactor surface). The absolute yields of N(2), N(2)O, H(2)O, and NH(3), which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH(3)-NO(2) (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO(3) itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO(3) in our kinetic modeling. The heterogeneous decomposition rate of HNO(3), HNO(3) + (B(2)O(3)/SiO(2)) --> OH + NO(2) + (B(2)O(3)/SiO(2)), was determined by varying its rate to match the modeled result to the measured concentrations of NH(3) and H(2)O; the rate could be represented by k(2b) = 7.91 x 10(7) exp(-12 600/T) s(-1), which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO(3) decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  1. Thermal Decomposition of Gaseous Ammonium Nitrate at Low Pressure: Kinetic Modeling of Product Formation and Heterogeneous Decomposition of Nitric Acid

    NASA Astrophysics Data System (ADS)

    Park, J.; Lin, M. C.

    2009-10-01

    The thermal decomposition of ammonium nitrate, NH4NO3 (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH4NO3 at 423 K was proposed to produce equal amounts of NH3 and HNO3, followed by the decomposition reaction of HNO3, HNO3 + M → OH + NO2 + M (where M = third-body and reactor surface). The absolute yields of N2, N2O, H2O, and NH3, which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH3-NO2 (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO3 itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO3 in our kinetic modeling. The heterogeneous decomposition rate of HNO3, HNO3 + (B2O3/SiO2) → OH + NO2 + (B2O3/SiO2), was determined by varying its rate to match the modeled result to the measured concentrations of NH3 and H2O; the rate could be represented by k2b = 7.91 × 107 exp(-12 600/T) s-1, which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO3 decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

  2. Graphene decorated microelectrodes for simultaneous detection of ascorbic, dopamine, and folic acids by means of chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Namdar, N.; Hassanpour Amiri, M.; Dehghan Nayeri, F.; Gholizadeh, A.; Mohajerzadeh, S.

    2015-09-01

    In this paper, high quality and large area graphene layers were synthesized using thermal chemical vapour deposition on copper foil substrates. We use graphene incorporated electrodes to measure simultaneously ascorbic acid, dopamine and folic acid. Cyclic voltammetry and differential pulse voltammetry methods were used to evaluate electrochemical behaviour of the grown graphene layers. The graphene-modified electrode shows large electrochemical potential difference compared to bare gold electrodes with higher current responses. Also our fabricated electrodes configuration can be used easily for microfluidic analysis.

  3. Incorporation of stratospheric acids into water ice

    NASA Technical Reports Server (NTRS)

    Elliott, Scott; Turco, Richard P.; Toon, Owen B.; Hamill, Patrick

    1990-01-01

    Hydrochloric and hydrofluoric acids are absorbed within the water ice lattice at mole fractions maximizing below 0.00001 and 0.0001 in a variety of solid impurity studies. The absorption mechanism may be substitutional or interstitial, leading in either case to a weak permeation of stratospheric ices by the acids at equilibrium. Impurities could also inhabit grain boundaries, and the acid content of atmospheric ice crystals will then depend on details of their surface and internal microstructures. Limited evidence indicates similar properties for the absorption of HNO3. Water ice lattices saturated with acid cannot be a significant local reservoir for HCl in the polar stratosphere.

  4. Modification of the surface chemistry of single- and multi-walled carbon nanotubes by HNO3 and H2SO4 hydrothermal oxidation for application in direct contact membrane distillation.

    PubMed

    Morales-Torres, Sergio; Silva, Tânia L S; Pastrana-Martínez, Luisa M; Brandão, Ana T S C; Figueiredo, José L; Silva, Adrián M T

    2014-06-28

    A specific methodology based on nitric acid hydrothermal oxidation was used to control the surface chemistry of multi-walled (MWCNTs) and single-walled (SWCNTs) carbon nanotubes (CNTs) with different lengths, and this methodology was adapted to the use of sulphuric acid containing ammonium persulfate as an oxidizing agent. The amount of oxygen-containing surface groups depends on the number and length of the graphene layers of the CNTs, thicker and shorter CNTs having more reactive sites for surface functionalization. In particular, the oxidation of MWCNTs was more pronounced than that of short SWCNTs and less surface groups were introduced into long SWCNTs, regardless of the acid used at any fixed concentration. It was also possible to tailor the surface chemistry of both SWCNTs and MWCNTs by using the adopted methodologies, and the amount of both oxygen- and sulphur-containing functional groups was correlated with the concentration of each oxidizing agent used. Mathematical functions that allow precise control of the amount and type of the surface groups introduced into carbon nanotubes were obtained. Buckypapers were also prepared over a polytetrafluoroethylene commercial membrane. These membranes were tested in direct contact membrane distillation and, under salinity conditions, the membrane prepared using oxidized MWCNTs (instead of SWCNTs) was the most efficient, the permeate flux of the commercial membrane significantly increasing in the presence of these CNTs, while completely rejecting chloride ions. In addition, the permeate flux was precisely correlated with the amount of oxygenated functional surface groups (as well as with the pH of point of zero charge) of the oxidized MWCNTs.

  5. Water vapor diffusion membranes, 2

    NASA Technical Reports Server (NTRS)

    Holland, F. F.; Klein, E.; Smith, J. K.; Eyer, C.

    1976-01-01

    Transport mechanisms were investigated for the three different types of water vapor diffusion membranes. Membranes representing porous wetting and porous nonwetting structures as well as dense diffusive membrane structures were investigated for water permeation rate as a function of: (1) temperature, (2) solids composition in solution, and (3) such hydrodynamic parameters as sweep gas flow rate, solution flow rate and cell geometry. These properties were measured using nitrogen sweep gas to collect the effluent. In addition, the chemical stability to chromic acid-stabilized urine was measured for several of each type of membrane. A technology based on the mechanism of vapor transport was developed, whereby the vapor diffusion rates and relative susceptibility of membranes to fouling and failure could be projected for long-term vapor recovery trials using natural chromic acid-stabilized urine.

  6. Microbial Community Structure and Arsenic Biogeochemistry in an Acid Vapor-Formed Spring in Tengchong Geothermal Area, China

    PubMed Central

    Jiang, Zhou; Li, Ping; Jiang, Dawei; Dai, Xinyue; Zhang, Rui; Wang, Yanhong; Wang, Yanxin

    2016-01-01

    Arsenic biogeochemistry has been studied extensively in acid sulfate-chloride hot springs, but not in acid sulfate hot springs with low chloride. In this study, Zhenzhuquan in Tengchong geothermal area, a representative acid sulfate hot spring with low chloride, was chosen to study arsenic geochemistry and microbial community structure using Illumina MiSeq sequencing. Over 0.3 million 16S rRNA sequence reads were obtained from 6-paired parallel water and sediment samples along its outflow channel. Arsenic oxidation occurred in the Zhenxhuquan pool, with distinctly high ratios of arsenate to total dissolved arsenic (0.73–0.86). Coupled with iron and sulfur oxidation along the outflow channel, arsenic accumulated in downstream sediments with concentrations up to 16.44 g/kg and appeared to significantly constrain their microbial community diversity. These oxidations might be correlated with the appearance of some putative functional microbial populations, such as Aquificae and Pseudomonas (arsenic oxidation), Sulfolobus (sulfur and iron oxidation), Metallosphaera and Acidicaldus (iron oxidation). Temperature, total organic carbon and dissolved oxygen significantly shaped the microbial community structure of upstream and downstream samples. In the upstream outflow channel region, most microbial populations were microaerophilic/anaerobic thermophiles and hyperthermophiles, such as Sulfolobus, Nocardia, Fervidicoccus, Delftia, and Ralstonia. In the downstream region, aerobic heterotrophic mesophiles and thermophiles were identified, including Ktedonobacteria, Acidicaldus, Chthonomonas and Sphingobacteria. A total of 72.41–95.91% unassigned-genus sequences were derived from the downstream high arsenic sediments 16S rRNA clone libraries. This study could enable us to achieve an integrated understanding on arsenic biogeochemistry in acid hot springs. PMID:26761709

  7. Microbial Community Structure and Arsenic Biogeochemistry in an Acid Vapor-Formed Spring in Tengchong Geothermal Area, China.

    PubMed

    Jiang, Zhou; Li, Ping; Jiang, Dawei; Dai, Xinyue; Zhang, Rui; Wang, Yanhong; Wang, Yanxin

    2016-01-01

    Arsenic biogeochemistry has been studied extensively in acid sulfate-chloride hot springs, but not in acid sulfate hot springs with low chloride. In this study, Zhenzhuquan in Tengchong geothermal area, a representative acid sulfate hot spring with low chloride, was chosen to study arsenic geochemistry and microbial community structure using Illumina MiSeq sequencing. Over 0.3 million 16S rRNA sequence reads were obtained from 6-paired parallel water and sediment samples along its outflow channel. Arsenic oxidation occurred in the Zhenxhuquan pool, with distinctly high ratios of arsenate to total dissolved arsenic (0.73-0.86). Coupled with iron and sulfur oxidation along the outflow channel, arsenic accumulated in downstream sediments with concentrations up to 16.44 g/kg and appeared to significantly constrain their microbial community diversity. These oxidations might be correlated with the appearance of some putative functional microbial populations, such as Aquificae and Pseudomonas (arsenic oxidation), Sulfolobus (sulfur and iron oxidation), Metallosphaera and Acidicaldus (iron oxidation). Temperature, total organic carbon and dissolved oxygen significantly shaped the microbial community structure of upstream and downstream samples. In the upstream outflow channel region, most microbial populations were microaerophilic/anaerobic thermophiles and hyperthermophiles, such as Sulfolobus, Nocardia, Fervidicoccus, Delftia, and Ralstonia. In the downstream region, aerobic heterotrophic mesophiles and thermophiles were identified, including Ktedonobacteria, Acidicaldus, Chthonomonas and Sphingobacteria. A total of 72.41-95.91% unassigned-genus sequences were derived from the downstream high arsenic sediments 16S rRNA clone libraries. This study could enable us to achieve an integrated understanding on arsenic biogeochemistry in acid hot springs.

  8. Evaluation of the Single Dilute (0.43 M) Nitric Acid Extraction to Determine Geochemically Reactive Elements in Soil

    PubMed Central

    2017-01-01

    Recently a dilute nitric acid extraction (0.43 M) was adopted by ISO (ISO-17586:2016) as standard for extraction of geochemically reactive elements in soil and soil like materials. Here we evaluate the performance of this extraction for a wide range of elements by mechanistic geochemical modeling. Model predictions indicate that the extraction recovers the reactive concentration quantitatively (>90%). However, at low ratios of element to reactive surfaces the extraction underestimates reactive Cu, Cr, As, and Mo, that is, elements with a particularly high affinity for organic matter or oxides. The 0.43 M HNO3 together with more dilute and concentrated acid extractions were evaluated by comparing model-predicted and measured dissolved concentrations in CaCl2 soil extracts, using the different extractions as alternative model-input. Mean errors of the predictions based on 0.43 M HNO3 are generally within a factor three, while Mo is underestimated and Co, Ni and Zn in soils with pH > 6 are overestimated, for which possible causes are discussed. Model predictions using 0.43 M HNO3 are superior to those using 0.1 M HNO3 or Aqua Regia that under- and overestimate the reactive element contents, respectively. Low concentrations of oxyanions in our data set and structural underestimation of their reactive concentrations warrant further investigation. PMID:28164700

  9. Nitric acid dry deposition to conifer forests: Niwot Ridge spruce-fir-pine study

    USGS Publications Warehouse

    Sievering, H.; Kelly, T.; McConville, G.; Seibold, C.; Turnipseed, A.

    2001-01-01

    The dry deposition velocity of nitric acid, Vd(HNO3), over a 12-m (mean height) spruce-fir forest at Niwot Ridge, Colorado was estimated during 13 daytime periods using the flux-gradient approach. Turbulence intensity at this site is high (mean u* of 0.65ms-1 with u of 2.9ms-1) and contributed to the large observed Vd(HNO3). The overriding contributor is identified to be the small aerodynamic needle width of the conifer trees. Two cases had inflated Vd(HNO3) due to height-differentiated nitric acid loss to soil-derived particle surfaces. Not considering these cases, the mean Vd(HNO3) was 7.6cms-1. The mean laminar boundary layer resistance (Rb) was found to be 7.8sm-1 (of similar magnitude to that of the aerodynamic resistance, 8.5sm-1). The data-determined Rb is bracketed by two theoretical estimates of the mean Rb, 5.9 and 8.6sm-1, that include consideration of the small canopy length scale (aerodynamic needle width), 1mm or less, at this conifer forest. However, the poor correlation of data-determined Rb values with both sets of theoretical estimates indicates that measurement error needs to be reduced and/or improved formulations of theoretical Rb values are in order. The large observed Vd(HNO3) at this conifer forest site is attributed to high turbulence intensity, and, especially, to small aerodynamic needle width. Copyright ?? 2001 Elsevier Science Ltd.

  10. The Consistency of Isotopologues of Ambient Atmospheric Nitric Acid in Passively Collected Samples

    NASA Astrophysics Data System (ADS)

    Bell, M. D.; Sickman, J. O.; Bytnerowicz, A.; Padgett, P.; Allen, E. B.

    2012-12-01

    Anthropogenic sources of nitrogen oxides have previously been shown to have distinctive isotopic signatures of oxygen and nitrogen. Nylon filters are currently used in passive sampling arrays to measure ambient atmospheric nitric acid concentrations and estimate deposition rates. This experiment measured the ability of nylon filters to consistently collect isotopologues of atmospheric nitric acid in the same ratios as they are present in the atmosphere. Samplers were deployed in continuous stirred tank reactors (CSTR) and at field sites across a nitrogen deposition gradient in Southern California. Filters were exposed over a four week period with individual filters being subjected to 1-4 week exposure times. Extracted nitric acid were measured for δ18O and δ15N ratios and compared for consistency based on length of exposure and amount of HNO3 collected. Filters within the CSTRs collected HNO3 at a consistent rate in both high and low concentration chambers. After two weeks of exposure, the mean δ18O values were within 0.5‰ of the δ18O of the source HNO3 solution. The mean of all weekly exposures were within 0.5‰ of the δ15N of the source solution, but after three weeks, the mean δ15N of adsorbed HNO3 was within 0.2‰. As the length of the exposure increased, the variability of measured delta values decreased for both elements. The field samplers collected HNO3 consistent with previously measured values along a deposition gradient. The mean δ18O at high deposition sites was 52.2‰ compared to 35.7‰ at the low deposition sites. Mean δ15N values were similar at all sites across the deposition gradient. Due to precipitation events occurring during the exposure period, the δ15N and δ18O of nitric acid were highly variable at all field sites. At single sites, changes in δ15N and δ18O were negatively correlated, consistent with two-sourcing mixing dynamics, but the slope of the regressions differed between high and low deposition sites. Anthropogenic

  11. A broadband cavity enhanced absorption spectrometer for aircraft measurements of glyoxal, methylglyoxal, nitrous acid, nitrogen dioxide, and water vapor

    NASA Astrophysics Data System (ADS)

    Min, K.-E.; Washenfelder, R. A.; Dubé, W. P.; Langford, A. O.; Edwards, P. M.; Zarzana, K. J.; Stutz, J.; Lu, K.; Rohrer, F.; Zhang, Y.; Brown, S. S.

    2016-02-01

    We describe a two-channel broadband cavity enhanced absorption spectrometer (BBCEAS) for aircraft measurements of glyoxal (CHOCHO), methylglyoxal (CH3COCHO), nitrous acid (HONO), nitrogen dioxide (NO2), and water (H2O). The instrument spans 361-389 and 438-468 nm, using two light-emitting diodes (LEDs) and a single grating spectrometer with a charge-coupled device (CCD) detector. Robust performance is achieved using a custom optical mounting system, high-power LEDs with electronic on/off modulation, high-reflectivity cavity mirrors, and materials that minimize analyte surface losses. We have successfully deployed this instrument during two aircraft and two ground-based field campaigns to date. The demonstrated precision (2σ) for retrievals of CHOCHO, HONO and NO2 are 34, 350, and 80 parts per trillion (pptv) in 5 s. The accuracy is 5.8, 9.0, and 5.0 %, limited mainly by the available absorption cross sections.

  12. A broadband cavity enhanced absorption spectrometer for aircraft measurements of glyoxal, methylglyoxal, nitrous acid, nitrogen dioxide, and water vapor

    NASA Astrophysics Data System (ADS)

    Min, K.-E.; Washenfelder, R. A.; Dubé, W. P.; Langford, A. O.; Edwards, P. M.; Zarzana, K. J.; Stutz, J.; Lu, K.; Rohrer, F.; Zhang, Y.; Brown, S. S.

    2015-10-01

    We describe a two-channel broadband cavity enhanced absorption spectrometer (BBCEAS) for aircraft measurements of glyoxal (CHOCHO), methylglyoxal (CH3COCHO), nitrous acid (HONO), nitrogen dioxide (NO2), and water (H2O). The instrument spans 361-389 and 438-468 nm, using two light emitting diodes (LEDs) and a grating spectrometer with a charge-coupled device (CCD) detector. Robust performance is achieved using a custom optical mounting system, high power LEDs with electronic on/off modulation, state-of-the-art cavity mirrors, and materials that minimize analyte surface losses. We have successfully deployed this instrument during two aircraft and two ground-based field campaigns to date. The demonstrated precision (2σ) for retrievals of CHOCHO, HONO and NO2 are 34, 350 and 80 pptv in 5 s. The accuracy is 5.8, 9.0 and 5.0 % limited mainly by the available absorption cross sections.

  13. Effect of acid vapor etching on morphological and opto-electric properties of flat silicon and silicon nanowire arrays: A comparative study

    NASA Astrophysics Data System (ADS)

    Amri, Chohdi; Ouertani, Rachid; Hamdi, Abderrahmen; Ezzaouia, Hatem

    2016-03-01

    In this paper, we report a comparative study between porous silicon (pSi) and porous silicon nanowires (pSiNWs). Acid Vapor Etching (AVE) treatment has been used to perform porous structure on flat Si and SiNWs array substrates respectively. SiNW structure is prepared by the widely used Silver catalyzed etching method. SEM and TEM images show that AVE treatment induces porous structure in the whole Si wafer and the SiNW sidewall. Comparatively to pSi, pSiNWs exhibit a low reflectivity in the whole spectral range which decreases with etching duration. However, the reflectivity of pSi changes with porous layer thickness. Both pSi and pSiNWs exhibit a significant PL peak situated at 2 eV. PL peaks are attributed to the quantum confinement effect in the silicon nanocrystallites (SiNCs). We discussed the significant enhancement in the peak intensities and a shift toward lower energy displayed in Raman spectra for both pSi and pSiNWs. We reported a correlative study of the AVE treatment effect on the minority carrier life time of flat silicon and SiNW arrays with the passivation effect of chemical induced silicon oxides highlighted by FTIR spectra.

  14. In situ synthesis of silver nanoparticles on the cotton fabrics modified by plasma induced vapor phase graft polymerization of acrylic acid for durable multifunction

    NASA Astrophysics Data System (ADS)

    Wang, C. X.; Ren, Y.; Lv, J. C.; Zhou, Q. Q.; Ma, Z. P.; Qi, Z. M.; Chen, J. Y.; Liu, G. L.; Gao, D. W.; Lu, Z. Q.; Zhang, W.; Jin, L. M.

    2017-02-01

    A practical and ecological method for preparing the multifunctional cotton fabrics with excellent laundering durability was explored. Cotton fabrics were modified by plasma induced vapor phase graft polymerization (PIVPGP) of acrylic acid (AA) and subsequently silver nanoparticles (AgNPs) were in situ synthesized on the treated cotton fabrics. The AgNP loaded cotton fabrics were characterized by scanning electron microscope (SEM), energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), antibacterial activity, self-cleaning activity, thermal stability and laundering durability, respectively. SEM observation and EDX, XPS and XRD analysis demonstrated the much more AgNPs deposition on the cotton fabrics modified by PIVPGP of AA. The AgNP loaded cotton fabrics also exhibited better antibacterial activity, self-cleaning activity, thermal stability and laundering durability. It was concluded that the surface modification of the cotton fabrics by PIVPGP of AA could increase the loading efficiency and binding fastness of AgNPs on the treated cotton fabrics, which could fabricate the cotton fabrics with durable multifunction. In addition, the mechanism of in situ synthesis of AgNPs on the cotton fabrics modified by PIVPGP of AA was proposed.

  15. Mobilization of Cr(VI) from chromite ore processing residue through acid treatment.

    PubMed

    Tinjum, James M; Benson, Craig H; Edil, Tuncer B

    2008-02-25

    Batch leaching studies on chromite ore processing residue (COPR) were performed using acids to investigate leaching of hexavalent chromium, Cr(VI), with respect to particle size, reaction time, and type of acid (HNO(3) and H(2)SO(4)). Aqueous Cr(VI) is maximized at approximately 0.04 mol Cr(VI) per kg of dry COPR at pH 7.6-8.1. Cr(VI) mobilized more slowly for larger particles, and the pH increased with time and increased more rapidly for smaller particles, suggesting that rate limitations occur in the solid phase. With H(2)SO(4), the pH stabilized at a higher value (8.8 for H(2)SO(4) vs. 8.0 for HNO(3)) and more rapidly (16 h vs. 30 h), and the differences in pH for different particle sizes were smaller. The acid neutralization capacity (ANC) of COPR is very large (8 mol HNO(3) per kg of dry COPR for a stable eluate pH of 7.5). Changes to the elemental and mineralogical composition and distribution in COPR particles after mixing with acid indicate that Cr(VI)-bearing solids dissolved. However, concentrations of Cr(VI) >2800 mg kg(-1) (>50% of the pre-treatment concentration) were still found after mixing with acid, regardless of the particle size, reaction time, or type of acid used. The residual Cr(VI) appears to be partially associated with poorly-ordered Fe and Al oxyhydroxides that precipitated in the interstitial areas of COPR particles. Remediation strategies that use HNO(3) or H(2)SO(4) to neutralize COPR or to maximize Cr(VI) in solution are likely to require extensive amounts of acid, may not mobilize all of the Cr(VI), and may require extended contact time, even under well-mixed conditions.

  16. XPS and STEM studies of Allende acid insoluble residues

    NASA Technical Reports Server (NTRS)

    Housley, R. M.; Clarke, D. R.

    1980-01-01

    Data on Allende acid residues obtained both before and after etching with hot HNO3 are presented. X-ray photoelectron spectra show predominantly carbonaceous material plus Fe-deficient chromite in both cases. The HNO3 oxidizes the carbonaceous material to some extent. The small chromites in these residues have a wide range of compositions somewhat paralleling those observed in larger Allende chromites and in Murchison chromites, especially in the high Al contents; however, they are deficient in divalent cations, which makes them metastable and indicates that they must have formed at relatively low temperatures. It is suggested that they formed by precipitation of Cr(3+) and Fe(3+) from olivine at low temperature or during rapid cooling.

  17. Thermal hazard evaluation of lauroyl peroxide mixed with nitric acid.

    PubMed

    Tsai, Lung-Chang; You, Mei-Li; Ding, Mei-Fang; Shu, Chi-Min

    2012-07-04

    Many thermal runaway incidents have been caused by organic peroxides due to the peroxy group, -O-O-, which is essentially unstable and active. Lauroyl peroxide (LPO) is also sensitive to thermal sources and is incompatible with many materials, such as acids, bases, metals, and ions. From the thermal decomposition reaction of various concentrations of nitric acid (HNO3) (from lower to higher concentrations) with LPO, experimental data were obtained as to its exothermic onset temperature (T0), heat of decomposition (ΔHd), isothermal time to maximum rate (TMRiso), and other safety parameters exclusively for loss prevention of runaway reactions and thermal explosions. As a novel finding, LPO mixed with HNO3 can produce the detonation product of 1-nitrododecane. We used differential scanning calorimetry (DSC), thermal activity monitor III (TAM III), and gas chromatography/mass spectrometer (GC/MS) analyses of the reactivity for LPO and itself mixed with HNO3 to corroborate the decomposition reactions and reaction mechanisms in these investigations.

  18. Laboratory measurements of heterogeneous reactions on sulfuric acid surfaces

    NASA Technical Reports Server (NTRS)

    Williams, Leah R.; Manion, Jeffrey A.; Golden, David M.; Tolbert, Margaret A.

    1994-01-01

    Increasing evidence from field, modeling, and laboratory studies suggests that heterogeneous reactions on stratospheric sulfate aerosol particles may contribute to global ozone depletion. Using a Knudsen cell reactor technique, the authors have studied the uptake, reactivity, and solubility of several trace atmospheric species on cold sulfuric acid surfaces representative of stratospheric aerosol particles. The results suggest that the heterogeneous conversion of N2O5 to HNO3 is fast enough to significantly affect the partitioning of nitrogen species in the global stratosphere and thus contribute to global ozone depletion. The hydrolysis of ClONO2 is slower and unlikely to be important under normal conditions at midlatitudes. The solubilities of HCl and HNO3 in sulfuric acid down to 200 K were found to be quite low. For HCl, this means that little HCl is available for reaction on the surfaces of stratospheric sulfate aerosol particles. The low solubility of HNO3 means that this product of heterogeneous reactions will enter the gas phase, and the denitrification observed in polar regions is unlikely to occur in the global stratosphere.

  19. Petroleum Vapor Intrusion

    EPA Pesticide Factsheets

    One type of vapor intrusion is PVI, in which vapors from petroleum hydrocarbons such as gasoline, diesel, or jet fuel enter a building. Intrusion of contaminant vapors into indoor spaces is of concern.

  20. New method of treating dilute mineral acids using magnesium-aluminum oxide.

    PubMed

    Kameda, Tomohito; Yabuuchi, Fumiko; Yoshioka, Toshiaki; Uchida, Miho; Okuwaki, Akitsugu

    2003-04-01

    Mineral acids, such as H(3)PO(4), H(2)SO(4), HCl, and HNO(3,) were treated with magnesium-aluminum oxide (Mg-Al oxide), which behaved as a neutralizer and fixative of anions. Anion removal increased with increasing Mg-Al oxide quantity, time, Mg/Al molar ratio, and initial acid concentration. Up to 95% removal of anions was achieved in 0.5 N acids using a stoichiometric quantity of Mg(0.80)Al(0.20)O(1.10) for H(3)PO(4), 1.75 stoichiometric quantities for H(2)SO(4), or 2.5 stoichiometric quantities for HCl or HNO(3) at 20 degrees C over a period of 6 h. The final solutions were found to have a pH in the range of 8-12. Selectivity of acid removal was found to follow the following order: H(3)PO(4) > H(2)SO(4) > HCl > HNO(3). The equivalent of acid removal per 1 g of Mg-Al oxide decreased as the Mg/Al molar ratio of Mg-Al oxide increased.

  1. Superfund Vapor Intrusion

    EPA Pesticide Factsheets

    In addition to basic information about vapor intrusion, the site contains technical and policy documents, tools and other resources to support vapor intrusion environmental investigations and mitigation activities.

  2. Heterogeneous reactions of chlorine nitrate and hydrogen chloride on type I polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Leu, Ming-Taun; Moore, Steven B.; Keyser, Leon F.

    1991-01-01

    A fast-flow reactor coupled with a quadrupole mass spectrometer was used to study the heterogeneous reactions ClONO2 + HCl yields Cl2 + HNO3 (1) and ClONO2 + H2O yields HOCl + HNO3 (2) on vapor-deposited HNO3-H2O ice substrates. It was found that the sticking coefficient of HCl on these substrates was a strong function of the substrate composition, ranging from about 2 x 10 exp -5 at nitric acid trihydrate composition to 6 x 10 exp -3 at 45 wt pct HNO3. The HNO3-H2O ice substrates were found to have large internal surface areas, and corrections for gas-phase diffusion within the porous ices were applied to observed loss rates.

  3. Isothermal Roll Forging of T55 Compressor Blades. Phase 2

    DTIC Science & Technology

    1980-06-01

    4. Descaled and passivated by a sequence through hot Kolene, HF-HNO3, HNO3 and water rinse. 5. The bars were lubricated with MAGNU DRAW 40* and...including: flash removal; lubricant removal; descaling ; etc. 4. Reduction in preparation for subsequent operation including: stress relief...the components were hot vapor degreased, etched in 50% nitric acid, de-smutted in concentrated hydrochloric acid, water rinsed and dried

  4. Effect of acid additives on sugarcane bagasse pyrolysis: Production of high yields of sugars.

    PubMed

    David, Geraldo Ferreira; Perez, Victor Haber; Rodriguez Justo, Oselys; Garcia-Perez, Manuel

    2017-01-01

    The aim of this work was to improve sugarcane bagasse thermochemical conversion to pyrolytic sugars production, particularly to levoglucosan. The experiments were carried out evaluating the effect of acid washing with HNO3 (0.1wt.%) followed by H2SO4 addition (0.1, 0.2 and 0.3wt.%) at pyrolysis temperatures of 350, 400, 450, 500, 550 and 600°C was studied by Py-GC/MS. The experimental results showed that HNO3 washing, followed by H2SO4 concentration of 0.2wt.% at 350°C resulted in an increase in levoglucosan yield between 5 and 7 times the yield obtained when the raw bagasse was processed. Thus, these results are very attractive to improve pyrolytic sugars production in sugarcane bagasse by previously acid treatment to pyrolysis technology.

  5. Enhancement of acidic gases in biomass burning impacted air masses over Canada

    NASA Technical Reports Server (NTRS)

    Lefer, B. L.; Talbot, R. W.; Harriss, R. C.; Bradshaw, J. D.; Sandholm, S. T.; Olson, J. O.; Sachse, G. W.; Collins, J.; Shipham, M. A.; Blake, D. R.

    1994-01-01

    Biomass-burning impacted air masses sampled over central and eastern Canada during the summer of 1990 as part of ABLE 3B contained enhanced mixing ratios of gaseous HNO3, HCOOH, CH3COOH, and what appears to be (COOH)2. These aircraft-based samples were collected from a variety of fresh burning plumes and more aged haze layers from different source regions. Values of the enhancement factor, delta X/delta CO, where X represents an acidic gas, for combustion-impacted air masses sampled both near and farther away from the fires, were relatively uniform. However, comparison of carboxylic acid emission ratios measured in laboratory fires to field plume enhancement factors indicates significant in-plume production of HCOOH. Biomass-burning appears to be an important source of HNO3, HCOOH, and CH3COOH to the troposphere over subarctic Canada.

  6. Nitric acid and ammonia emissions from a mid-latitude prescribed wetlands fire

    NASA Technical Reports Server (NTRS)

    Lebel, P. J.; Cofer, W. R., III; Levine, J. S.; Vay, S. A.; Roberts, P. D.

    1988-01-01

    The first simultaneous measurements of gaseous nitric acid and ammonia in the smoke plume of a wetlands biomass burn were obtained. The measurements were made using tungsten oxide-coated diffusion denuder tubes from a helicopter during a prescribed burn on November 9, 1987, at the Merritt Island National Wildlife Refuge, located at the NASA John F. Kennedy Space Center, Florida. The mean NH3 and HNO3 mixing ratios measured in the smoke plume were 19 ppbv and 14 ppbv, respectively, both significantly higher than background mixing ratios. Nitric acid correlated well with carbon dioxide produced by the combustion. The mean CO2-normalized emission ratio for HNO3 was found to be 0.00012. Ammonia, however, dit not correlate well with CO2, suggesting a more complex relationship between combustion and production/release of NH3.

  7. Densities and apparent molar volumes of atmospherically important electrolyte solutions. 1. The solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl from 0 to 50 °C, including extrapolations to very low temperature and to the pure liquid state, and NaHSO4, NaOH, and NH3 at 25 °C.

    PubMed

    Clegg, S L; Wexler, A S

    2011-04-21

    Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H(2)SO(4), HNO(3), HCl, Na(2)SO(4), NaNO(3), NaCl, (NH(4))(2)SO(4), NH(4)NO(3), and NH(4)Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg(-1), it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm(3) mol(-1) from 0 to 50 °C. Volume properties of aqueous NaHSO(4), NaOH, and NH(3) have also been evaluated, at 25 °C only. In part 2 of this work (ref 1 ) an ion interaction (Pitzer

  8. Interaction of Peroxynitric Acid with Solid H2O Ice

    NASA Technical Reports Server (NTRS)

    Li, Zhuangjie; Friedl, Randall R.; Moore, Steven B.; Sander, Stanley P.

    1996-01-01

    The uptake of peroxynitric acid (PNA), HO2NO2 or HNO4, on solid H2O ice at 193 K (-80 C) was studied using a fast flow-mass spectrometric technique. An uptake coefficient of 0.15 +/- 0.10 was measured, where the quoted uncertainty denotes 2 standard deviations. The uptake process did not result in the production of gas phase products. The composition of the condensed phase was investigated using programmed heating (3 K/min) of the substrate coupled with mass spectrometric detection of desorbed species. Significant quantities of HNO, and HNO3 desorbed from the substrates at temperatures above 225 K and 246 K, respectively. The desorbed HNO3, which was less than 9% of the desorbed HNO, and remained unchanged upon incubation of the substrate, was likely due to impurities in the HNO4 samples rather than reaction of HNO, on the substrate. The onset temperatures for HNO4 desorption increased with increasing H2O to HNO4 ratios, indicating that HNO4, like HNO3, tends to be hydrated in the presence of water. These observations suggest possible mechanisms for removal of HNO4 or repartitioning of total odd nitrogen species in the Earth's upper troposphere and stratosphere.

  9. Heterogeneous conversion of calcite aerosol by nitric acid.

    PubMed

    Preszler Prince, A; Grassian, V H; Kleiber, P; Young, M A

    2007-02-07

    The reaction of nitric acid with calcite aerosol at varying relative humidities has been studied under suspended particle conditions in an atmospheric reaction chamber using infrared absorption spectroscopy. The reactant concentration in the chamber, as well as the appearance of gas phase products and surface adsorbed species, was spectroscopically monitored before and after mixing with CaCO(3) (calcite) particles. The interaction with HNO(3) was found to lead to gas phase CO(2) evolution and increased water uptake due to heterogeneous conversion of the carbonate to particulate nitrate. The reaction was enhanced as the relative humidity of the system was increased, especially at relative humidities above the reported deliquescence point of particulate Ca(NO(3))(2). The measured reaction extent demonstrates that the total calcite particulate mass is available for reaction with HNO(3) and the conversion process is not limited to the particle surface. The spectroscopy of the surface formed nitrate suggests a highly concentrated solution environment with a significant degree of ion pairing. The implications of the HNO(3) loss and the formation of the particulate nitrate product for atmospheric chemistry are discussed.

  10. Calibrated vapor generator source

    DOEpatents

    Davies, J.P.; Larson, R.A.; Goodrich, L.D.; Hall, H.J.; Stoddard, B.D.; Davis, S.G.; Kaser, T.G.; Conrad, F.J.

    1995-09-26

    A portable vapor generator is disclosed that can provide a controlled source of chemical vapors, such as, narcotic or explosive vapors. This source can be used to test and calibrate various types of vapor detection systems by providing a known amount of vapors to the system. The vapor generator is calibrated using a reference ion mobility spectrometer. A method of providing this vapor is described, as follows: explosive or narcotic is deposited on quartz wool, placed in a chamber that can be heated or cooled (depending on the vapor pressure of the material) to control the concentration of vapors in the reservoir. A controlled flow of air is pulsed over the quartz wool releasing a preset quantity of vapors at the outlet. 10 figs.

  11. Calibrated vapor generator source

    DOEpatents

    Davies, John P.; Larson, Ronald A.; Goodrich, Lorenzo D.; Hall, Harold J.; Stoddard, Billy D.; Davis, Sean G.; Kaser, Timothy G.; Conrad, Frank J.

    1995-01-01

    A portable vapor generator is disclosed that can provide a controlled source of chemical vapors, such as, narcotic or explosive vapors. This source can be used to test and calibrate various types of vapor detection systems by providing a known amount of vapors to the system. The vapor generator is calibrated using a reference ion mobility spectrometer. A method of providing this vapor is described, as follows: explosive or narcotic is deposited on quartz wool, placed in a chamber that can be heated or cooled (depending on the vapor pressure of the material) to control the concentration of vapors in the reservoir. A controlled flow of air is pulsed over the quartz wool releasing a preset quantity of vapors at the outlet.

  12. Heterogeneous Reactions of ClONO2, HCl, and HOCl on Liquid Sulfuric Acid Surfaces

    NASA Technical Reports Server (NTRS)

    Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

    1994-01-01

    The heterogeneous reactions of ClONO2 + H2O yields HNO3 + HOCl (1), ClONO2 + HCl yields C12 + HNO3 (2), and HOCl + HCl yields Cl2 + H2O (3) on liquid sulfuric acid surfaces have been studied using a fast flow reactor coupled to a quadrupole mass spectrometer. The main objectives of the study are to investigate: (a) the temperature dependence of these reactions at a fixed H2O partial pressure typical of the lower stratosphere (that is, by changing temperature at a constant water partial pressure, the H2SO4 content of the surfaces is also changed), (b) the relative importance or competition between reactions 1 and 2, and (c) the effect of HNO3 on the reaction probabilities due to the formation of a H2SO4/HNO3/H2O ternary system. The measurements show that all the reactions depend markedly on temperature at a fixed H2O partial pressure: they proceed efficiently at temperatures near 200 K and much slower at temperatures near 220 K. The reaction probability (gamma(sub 1)) for ClONO2 hydrolysis approaches 0.01 at temperatures below 200 K, whereas the values for gamma(sub 2) and gamma(sub 3) are on the order of a few tenths at 200 K. Although detailed mechanisms for these reactions are still unknown, the present data indicate that the competition between ClONO2 hydrolysis and ClONO2 reaction with HCl may depend on temperature (or H2SO4 Wt %): in the presence of gaseous HCl at stratospheric concentrations, reaction 2 is dominant at lower temperatures (less than 200 K), but reaction 1 becomes important at temperatures above 210 K. Furthermore, reaction probability measurements performed on the H2SO4/HNO3/ H2O ternary solutions do not exhibit noticeable deviation from those performed on the H2SO4/H2O binary system, suggesting little effect of HNO3 in sulfate aerosols on the ClONO2 and HOCl reactions with HCl. The results reveal that significant reductions in the chlorine-containing reservoir species (such as ClONO2 and HCl) can take place on stratospheric sulfate aerosols at

  13. Long-term variations in abundance and distribution of sulfuric acid vapor in the Venus atmosphere inferred from Pioneer Venus and Magellan radio occultation studies

    NASA Technical Reports Server (NTRS)

    Jenkins, J. M.; Steffes, P. G.

    1992-01-01

    Radio occultation experiments have been used to study various properties of planetary atmospheres, including pressure and temperature profiles, and the abundance profiles of absorbing constituents in those planetary atmospheres. However, the reduction of amplitude data from such experiments to determine abundance profiles requires the application of the inverse Abel transform (IAT) and numerical differentiation of experimental data. These two operations preferentially amplify measurement errors above the true signal underlying the data. A new technique for processing radio occultation data has been developed that greatly reduces the errors in the derived absorptivity and abundance profiles. This technique has been applied to datasets acquired from Pioneer Venus Orbiter radio occultation studies and more recently to experiments conducted with the Magellan spacecraft. While primarily designed for radar studies of the Venus surface, the high radiated power (EIRP) from the Magellan spacecraft makes it an ideal transmitter for measuring the refractivity and absorptivity of the Venus atmosphere by such experiments. The longevity of the Pioneer Venus Orbiter has made it possible to study long-term changes in the abundance and distribution of sulfuric acid vapor, H2SO4(g), in the Venus atmosphere between 1979 and 1992. The abundance of H2SO4(g) can be inferred from vertical profiles of 13-cm absorptivity profiles retrieved from radio occultation experiments. Data from 1979 and 1986-87 suggest that the abundance of H2SO4(g) at latitudes northward of 70 deg decreased over this time period. This change may be due to a period of active volcanism in the late 1970s followed by a relative quiescent period, or some other dynamic process in the Venus atmosphere. While the cause is not certain, such changes must be incorporated into dynamic models of the Venus atmosphere. Potentially, the Magellan spacecraft will extend the results of Pioneer Venus Orbiter and allow the continued

  14. Acid sulfate alteration of fluorapatite, basaltic glass and olivine by hydrothermal vapors and fluids: Implications for fumarolic activity and secondary phosphate phases in sulfate-rich Paso Robles soil at Gusev Crater, Mars

    NASA Astrophysics Data System (ADS)

    Hausrath, E. M.; Golden, D. C.; Morris, R. V.; Agresti, D. G.; Ming, D. W.

    2013-01-01

    Phosphate-rich rocks and a nearby phosphate-rich soil, Paso Robles, were analyzed in Gusev Crater, Mars, by the Mars Exploration Rover Spirit and interpreted to be highly altered, possibly by hydrothermal or fumarolic alteration of primary, phosphate-rich material. To test mineral phases resulting from such alteration, we performed hydrothermal acid-vapor and acid-fluid experiments on olivine (Ol), fluorapatite (Ap), and basaltic glass (Gl) as single phases and a mixture of phases. Minerals formed include Ca-, Al-, Fe- and Mg-sulfates with different hydration states (anhydrite, bassanite, gypsum; alunogen; hexahydrite, and pentahydrite). Phosphate-bearing minerals formed included monocalcium phosphate monohydrate (MCP) (acid-vapor and acid-fluid alteration of fluorapatite only) and ferrian giniite (acid-fluid alteration of the Ol + Gl + Ap mixture). MCP is likely present in Paso Robles if primary Ca-phosphate minerals reacted with sulfuric acid with little transport of phosphate. Under fluid:rock ratios allowing transport of phosphate, a ferric phosphate phase such as ferrian giniite might form instead. Mössbauer measurements of ferrian giniite-bearing alteration products and synthetic ferrian giniite are consistent with Spirit's Mössbauer measurements of the ferric-bearing phase in Paso Robes soil, but are also consistent with ferric sulfate phases in the low-P soil Arad_Samra. Therefore, Mössbauer data alone do not constrain the fluid:rock ratio. However, the excess iron (hematite) in Paso Robles soil, which implies aqueous transport, combined with our laboratory experiments, suggest acid-sulfate alteration in a hydrothermal (fumarolic) environment at fluid:rock ratios sufficient to allow dissolution, transport, and precipitation of secondary chemical components including a ferric phosphate such as ferrian giniite.

  15. The use of electrothermal vaporizer coupled to the inductively coupled plasma mass spectrometry for the determination of arsenic, selenium and transition metals in biological samples treated with formic acid.

    PubMed

    Tormen, Luciano; Gil, Raul A; Frescura, Vera L A; Martinez, Luis Dante; Curtius, Adilson J

    2012-03-02

    A fast method for the determination of As, Co, Cu, Fe, Mn, Ni, Se and V in biological samples by ETV-ICP-MS, after a simple sample treatment with formic acid, is proposed. Approximately 75 mg of each sample is mixed with 5 mL of formic acid, kept at 90°C for 1 h and then diluted with nitric acid aqueous solution to a 5% (v/v) formic acid and 1% (v/v) nitric acid final concentrations. A palladium solution was used as a chemical modifier. The instrumental conditions, such as carrier gas flow rate, RF power, pyrolysis and vaporization temperatures and argon internal flow rate during vaporization were optimized. The formic acid causes a slight decrease of the analytes signal intensities, but does not increase the signal of the mainly polyatomic ions ((14)N(35)Cl(+), (14)N(12)C(+), (40)Ar(12)C(+), (13)C(37)Cl(+), (40)Ar(36)Ar(+), (40)Ar(35)Cl(+), (35)Cl(16)O(+), (40)Ar(18)O(+)) that affect the analytes signals. The effect of charge transfer reactions, that could increase the ionization efficiency of some elements with high ionization potentials was not observed due to the elimination of most of the organic compounds during the pyrolysis step. External calibration with aqueous standard solutions containing 5% (v/v) formic acid allows the simultaneous determination of all analytes with high accuracy. The detection limits in the samples were between 0.01 (Co) and 850 μg kg(-1) (Fe and Se) and the precision expressed by the relative standard deviations (RSD) were between 0.1% (Mn) and 10% (Ni). Accuracy was validated by the analysis of four certified reference biological materials of animal tissues (lobster hepatopancreas, dogfish muscle, oyster tissue and bovine liver). The recommended procedure avoids plasma instability, carbon deposit on the cones and does not require sample digestion.

  16. Ultrafine aerosol size distributions and sulfuric acid vapor pressures: Implications for new particle formation in the atmosphere. Year 2 progress report

    SciTech Connect

    McMurry, P.H.

    1993-07-01

    This project has two components: (1) measurement of H{sub 2}SO{sub 4} vapor pressures in air under temperature/relative humidity conditions similar to atmospheric, and (2) measurement of ultrafine aerosol size distributions. During Year 2, more effort was put on size distribution measurements. 4 figs.

  17. Fourier transform infrared studies of model polar stratospheric cloud surfaces - Growth and evaporation of ice and nitric acid/ice

    NASA Technical Reports Server (NTRS)

    Tolbert, Margaret A.; Middlebrook, Ann M.

    1990-01-01

    Fourier-transform infrared surface studies are used to probe the microphysical properties of nitric acid trihydrate (NAT) and ice films representative of type I and II polar stratospheric clouds (PSC). Experiments indicate that, on initial exposure to 1.8 microtorr of HNO3, a layer of ice is quantitatively converted to NAT. However, conversion of ice to NAT does not proceed indefinitely, but rather the system reaches saturation. For longer exposures or higher HNO3 pressures, NAM becomes the dominant nitric acid containing species on the surface. Evaporation studies were performed to test the feasibility of a recent denitrification mechanism. The results indicate that ice coated with 0.20 micron of NAT evaporates at a temperature of about 4 C higher than uncoated ice.

  18. Wintertime nitric acid chemistry - Implications from three-dimensional model calculations

    NASA Technical Reports Server (NTRS)

    Rood, Richard B.; Kaye, Jack A.; Douglass, Anne R.; Allen, Dale J.; Steenford, Stephen

    1990-01-01

    A three-dimensional simulation of the evolution of HNO3 has been run for the winter of 1979. Winds and temperatures are taken from a stratospheric data assimilation analysis, and the chemistry is based on Limb Infrared Monitor of the Stratosphere (LIMS) observations. The model is compared to LIMS observations to investigate the problem of 'missing' nitric acid chemistry in the winter hemisphere. Both the model and observations support the contention that a nitric acid source is needed outside of the polar vortex and north of the subtropics. Observations suggest that HNO3 is not dynamically controlled in middle latitudes. The model shows that given the time scales of conventional chemistry, dynamical control is expected. Therefore, an error exists in the conventional chemistry or additional processes are needed to bring the model and data into agreement. Since the polar vortex is dynamically isolated from the middle latitudes, and since the highest HNO3 values are observed in October and November, a source associated solely with polar stratospheric clouds cannot explain the deficiencies in the chemistry. The role of heterogeneous processes on background aerosols is reviewed in light of these results.

  19. Timescale for hygroscopic conversion of calcite mineral particles through heterogeneous reaction with nitric acid.

    PubMed

    Sullivan, Ryan C; Moore, Meagan J K; Petters, Markus D; Kreidenweis, Sonia M; Roberts, Greg C; Prather, Kimberly A

    2009-09-28

    Atmospheric heterogeneous reactions can potentially change the hygroscopicity of atmospheric aerosols as they undergo chemical aging processes in the atmosphere. A particle's hygroscopicity influences its cloud condensation nuclei (CCN) properties with potential impacts on cloud formation and climate. In this study, size-selected calcite mineral particles were reacted with controlled amounts of nitric acid vapour over a wide range of relative humidities in an aerosol flow tube to study the conversion of insoluble and thus apparently non-hygroscopic calcium carbonate into soluble and hygroscopic calcium nitrate. The rate of hygroscopic change particles undergo during a heterogeneous reaction is derived from experimental measurements for the first time. The chemistry of the reacted particles was determined using an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS) while the particles' hygroscopicity was determined through measuring CCN activation curves fit to a single parameter of hygroscopicity, kappa. The reaction is rapid, corresponding to atmospheric timescales of hours. At low to moderate HNO3 exposures, the increase in the hygroscopicity of the particles is a linear function of the HNO3(g) exposure. The experimentally observed conversion rate was used to constrain a simple but accurate kinetic model. This model predicts that calcite particles will be rapidly converted into hygroscopic particles (kappa>0.1) within 4 h for low HNO3 mixing ratios (10 pptv) and in less than 3 min for 1000 pptv HNO3. This suggests that the hygroscopic conversion of the calcite component of atmospheric mineral dust aerosol will be controlled by the availability of nitric acid and similar reactants, and not by the atmospheric residence time.

  20. EPA Method 245.2: Mercury (Automated Cold Vapor Technique)

    EPA Pesticide Factsheets

    Method 245.2 describes procedures for preparation and analysis of drinking water samples for analysis of mercury using acid digestion and cold vapor atomic absorption. Samples are prepared using an acid digestion technique.

  1. Resistance properties of a macroporous silica-based N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide-impregnated polymeric adsorption material against nitric acid, temperature and γ-irradiation

    NASA Astrophysics Data System (ADS)

    Zhang, Anyun; Wei, Yuezhou; Hoshi, Harutaka; Kumagai, Mikio; Kamiya, Masayoshi; Koyama, Tomozo

    2005-04-01

    The resistance of a novel silica-based N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) polymeric adsorption material (TODGA/SiO 2-P) against nitric acid, temperature and γ-irradiation had been investigated. The adsorption property of the treated TODGA/SiO 2-P was evaluated by a 3 M HNO 3 solution containing 0.01 M Nd(III). It was found that both 3 and 0.01 M HNO 3 concentrations did not decrease the stability of TODGA/SiO 2-P at 25°C. The quantity of TODGA leaked from TODGA/SiO 2-P was equivalent to its solubility in the corresponding HNO 3 aqueous solution. The effect of 3 M HNO 3 on the leakage of TODGA at 80°C was significantly higher than that in 0.01 M HNO 3 as well as in all cases at 25°C. The amount of Nd(III) adsorbed towards the treated TODGA/SiO 2-P was determined in the range of 0.143-0.148 mmol/g for the HNO 3 concentration effect and 0.142-0.0506 mmol/g for the temperature effect. γ-Irradiation showed a more noticeable destruction effect on TODGA/SiO 2-P. The content of TODGA leaked increased with an increase in the γ-irradiation dose (ID) from 1.06 to 3.72 MGy in terms of the linear equation [TODGA]=794.5ID+84.0. The amount of Nd(III) adsorbed onto the irradiated TODGA/SiO 2-P decreased rapidly from 0.134 to 0.0438 mmol/g, which was lower than 0.153 mmol/g, the adsorption of fresh TODGA/SiO 2-P for Nd(III), according to the equation QNd(III)=-0.0301ID+0.160, showing that a large quantity of TODGA leaked from TODGA/SiO 2-P. The adsorbed amount of Nd(III) decreased obviously in this order: the HNO 3 concentration effect, temperature effect and γ-irradiation.

  2. Acid Rain

    USGS Publications Warehouse

    Bricker, Owen P.; Rice, Karen C.

    1993-01-01

    Acid deposition, or acid rain as it is more commonly referred to, has become a widely publicized environmental issue in the U.S. over the past decade. The term usually conjures up images of fish kills, dying forests, "dead" lakes, and damage to monuments and other historic artifacts. The primary cause of acid deposition is emission of S02 and NOx to the atmosphere during the combustion of fossil fuels. Oxidation of these compounds in the atmosphere forms strong acids - H2SO4 and HNO3 - which are returned to the Earth in rain, snow, fog, cloud water, and as dry deposition.Although acid deposition has only recently been recognized as an environmental problem in the U.S., it is not a new phenomenon (Cogbill & Likens 1974). As early as the middle of the 17th century in England, the deleterious effects of industrial emissions on plants, animals, and humans, and the atmospheric transport of pollutants between England and France had become issues of concern (Evelyn 1661, Graunt 1662). It is interesting that well over three hundred years ago in England, recommendations were made to move industry outside of towns and build higher chimneys to spread the pollution into "distant parts." Increasing the height of smokestacks has helped alleviate local problems, but has exacerbated others. In the U.S. the height of the tallest smokestack has more than doubled, and the average height of smokestacks has tripled since the 1950s (Patrick et al 1981). This trend occurred in most industrialized nations during the 20th century and has had the effect of transforming acid rain from a local urban problem into a problem of global scale.

  3. Acid Rain

    USGS Publications Warehouse

    Bricker, Owen P.; Rice, Karen C.; Dietrich, W.E.; Sposito, Garrison

    1997-01-01

    Acid deposition, or acid rain as it is more commonly referred to, has become a widely publicized environmental issue in the U.S. over the past decade. The term usually conjures up images of fish kills, dying forests, "dead" lakes, and damage to monuments and other historic artifacts. The primary cause of acid deposition is emission of S02 and NOx to the atmosphere during the combustion of fossil fuels. Oxidation of these compounds in the atmosphere forms strong acids - H2SO4 and HNO3 - which are returned to the Earth in rain, snow, fog, cloud water, and as dry deposition.Although acid deposition has only recently been recognized as an environmental problem in the U.S., it is not a new phenomenon (Cogbill & Likens 1974). As early as the middle of the 17th century in England, the deleterious effects of industrial emissions on plants, animals, and humans, and the atmospheric transport of pollutants between England and France had become issues of concern (Evelyn 1661, Graunt 1662). It is interesting that well over three hundred years ago in England, recommendations were made to move industry outside of towns and build higher chimneys to spread the pollution into "distant parts." Increasing the height of smokestacks has helped alleviate local problems, but has exacerbated others. In the U.S. the height of the tallest smokestack has more than doubled, and the average height of smokestacks has tripled since the 1950s (Patrick et al 1981). This trend occurred in most industrialized nations during the 20th century and has had the effect of transforming acid rain from a local urban problem into a problem of global scale.

  4. Interactions of Gas-Phase Nitric/Nitrous Acids and Primary Organic Aerosol in the Atmosphere of Houston, TX

    NASA Astrophysics Data System (ADS)

    Ziemba, L. D.; Griffin, R. J.; Dibb, J. E.; Anderson, C. H.; Whitlow, S. I.; Lefer, B. L.; Flynn, J.; Rappenglück, B.

    2007-12-01

    Concentrations of aerosol and gas-phase pollutants were measured on the roof of an 18-story building during the Texas Air Quality Study II Radical and Aerosol Measurement Project (TRAMP) from August 15 through September 28, 2006. Aerosol measurements included size-resolved, non-refractory mass concentrations of ammonium, nitrate, sulfate, chloride, and organic aerosol in submicron particles using an Aerodyne quadrupole aerosol mass spectrometer (Q-AMS). Particulate water-soluble organic carbon (PWSOC) was quantified using a mist chamber/total organic carbon analysis system. Concentration data for gas-phase pollutants included those for nitric acid (HNO3), nitrous acid (HONO), and hydrochloric acid (HCl) collected using a mist chamber/ion chromatographic technique, oxides of nitrogen (NOx) collected using a chemiluminescent method, and carbon monoxide (CO) collected using an infrared gas correlation wheel instrument. Coincident increases in nitrate and organic aerosol mass concentrations were observed on many occasions throughout the measurement campaign, most frequently during the morning rush hour. Based on the lack of organic aerosol processing (defined by the ratio of m/z = 44/57 in the Q-AMS spectra), strong correlation with NOx and CO, and a lack of significant increase in PWSOC concentration, the spikes in organic aerosol were likely associated with primary organic aerosol (POA). During these events, gas-phase HNO3 concentration decreases were observed simultaneously with increases in gas-phase HONO concentrations. These data likely indicate uptake of HNO3 and subsequent heterogeneous conversion to HONO involving POA. Preliminary calculations show that HNO3 partitioning could account for the majority of the observed HONO and aerosol nitrate concentrations during these events. Q-AMS chloride and HCl data also indicate uptake of chloride by particles during these events. This phenomenon was also observed during the night, but these nocturnal events were less

  5. Vapor phase pyrolysis

    NASA Technical Reports Server (NTRS)

    Steurer, Wolfgang

    1992-01-01

    The vapor phase pyrolysis process is designed exclusively for the lunar production of oxygen. In this concept, granulated raw material (soil) that consists almost entirely of metal oxides is vaporized and the vapor is raised to a temperature where it dissociates into suboxides and free oxygen. Rapid cooling of the dissociated vapor to a discrete temperature causes condensation of the suboxides, while the oxygen remains essentially intact and can be collected downstream. The gas flow path and flow rate are maintained at an optimum level by control of the pressure differential between the vaporization region and the oxygen collection system with the aid of the environmental vacuum.

  6. Stratospheric water vapor feedback.

    PubMed

    Dessler, A E; Schoeberl, M R; Wang, T; Davis, S M; Rosenlof, K H

    2013-11-05

    We show here that stratospheric water vapor variations play an important role in the evolution of our climate. This comes from analysis of observations showing that stratospheric water vapor increases with tropospheric temperature, implying the existence of a stratospheric water vapor feedback. We estimate the strength of this feedback in a chemistry-climate model to be +0.3 W/(m(2)⋅K), which would be a significant contributor to the overall climate sensitivity. One-third of this feedback comes from increases in water vapor entering the stratosphere through the tropical tropopause layer, with the rest coming from increases in water vapor entering through the extratropical tropopause.

  7. Laboratory studies on the retention of nitric acid, hydrochloric acid and ammonia on aerosol filters

    NASA Astrophysics Data System (ADS)

    Keck, Lothar; Wittmaack, Klaus

    Retention efficiencies of nitric acid, hydrochloric acid and ammonia were measured for different filters, with particular emphasis on cellulose (CE) and cellulose acetate-nitrate (CA) materials. Gases were produced either by nebulising aqueous solutions or by a novel technique based on the desorption from ammonium salts deposited on quartz fibre (QF) filters. Efficiencies for pure acidic gases and ammonia on CE and CA ranged from very low (⩽3.6%) to low (˜10% for HNO 3 on CE). In contrast, if acidic gases and ammonia were supplied in equimolar concentrations, they were retained (almost) completely on CE, with high efficiency on CA (60-80% for NH 3+HNO 3; 20-45% for NH 3+HCl), also with high efficiency on glass fibre filter, but with very low efficiency on QF and Teflon (Tf) filters (<1%). For CA, retention efficiencies were found to increase with increasing relative humidity and to decrease with decreasing mean pressure at which the filters were exposed to the gases. Once retained on CA filters, the retained gases may be lost again during subsequent exposure to clean air.

  8. Secondary acidification: Changes in gas-aerosol partitioning of semivolatile nitric acid and enhancement of its deposition due to increased emission and concentration of SOx

    NASA Astrophysics Data System (ADS)

    Kajino, Mizuo; Ueda, Hiromasa; Nakayama, Shinji

    2008-02-01

    Secondary acidification, or the indirect enhancement of semivolatile air pollutant deposition associated with increased SO42- concentrations, is shown to occur in general air pollution using data collected from six stations of the Acid Deposition Monitoring Network in East Asia (EANET) in Japan. This effect was first detected as a result of volcanic SO2 plumes in our previous studies. Results indicate that as SO42- concentration increases, gas-aerosol partitioning of nitric acid shifts to the gas phase, increasing the HNO3 gas concentration. Since the dry and wet deposition rates of HNO3 gas are very high, deposition can be enhanced even when the emission of NOx remains unchanged. In western Japan, the indirect effect for wet deposition is most apparent from spring to autumn, when the Asian continental outflow carries sulfate-rich contaminated air masses. However, it is not pronounced in air masses containing abundant sea-salt particles and related cation components in aerosols. In areas such as forests or farmlands with low surface resistance, dry deposition of nitric acid is more pronounced than wet deposition as the dry deposition velocity of HNO3 gas is high. Increased dry deposition of t-NO3 due to the indirect effect and consequent vegetation damage is thus of considerable concern in such regions. The deposition of other semivolatile components, such as hydrochloric acid and ammonia, can be altered and can also induce secondary acidification.

  9. The Effects of Gaseous Ozone and Nitric Acid Deposition on two Crustose Lichen Species From Joshua Tree National Park

    NASA Astrophysics Data System (ADS)

    Hessom, Elizabeth Curie

    Lichens are dependent on atmospheric deposition for much of their water and nutrients, and due to their sensitivity to pollutants, are commonly used as bioindicators for air quality. While studies have focused on epiphytic (tree dwelling) lichens as bioindicators, virtually nothing is known about crustose (rock dwelling) lichens. The atmospheric pollutants ozone (O 3) and nitric acid (HNO3) are two major pollutants found within the Los Angeles Basin. While recent O3 research suggests it does not significantly affect lichen growth, HNO3 appears to be phytotoxic to some lichens. As both of these pollutants are deposited downwind from the L.A. basin into Joshua Tree National Park (JOTR), lichen species located in the park may provide a sensitive indicator of pollution effects. This research studied two lichen species of particular interest from Joshua Tree National Park, Lobothallia praeradiosa (Nyl.) Hafellner, and Acarospora socialis H. Magn., both of which are crustose species with unknown sensitivities to O3, as well as hypothesized and unknown sensitivities to nitrogen compounds, respectively. Little research exists for either species, possibly because of the difficulty in working with crustose lichens. This research attempted to expand the background knowledge of these species by exposing them to varying levels of O3 and HNO3, to ascertain their physiological responses. Physiological measures of chlorophyll fluorescence, dark respiration, microscopic imaging, and lichen washes (as a proxy for membrane leakage), were measured throughout the exposure period. Results indicated that both species had similar sensitivities to O3 and HNO3. Both species registered physical damage during the O3 fumigation, as well as a decrease in respiration. Neither species showed major physical damage to HNO3, but both manifested a decrease in chlorophyll fluorescence, suggesting damage to the photosynthetic systems of the algae symbiont. These results suggest that both of these

  10. Application of hydrocyanic acid vapor generation via focused microwave radiation to the preparation of industrial effluent samples prior to free and total cyanide determinations by spectrophotometric flow injection analysis.

    PubMed

    Quaresma, Maria Cristina Baptista; de Carvalho, Maria de Fátima Batista; Meirelles, Francis Assis; Santiago, Vânia Maria Junqueira; Santelli, Ricardo Erthal

    2007-02-01

    A sample preparation procedure for the quantitative determination of free and total cyanides in industrial effluents has been developed that involves hydrocyanic acid vapor generation via focused microwave radiation. Hydrocyanic acid vapor was generated from free cyanides using only 5 min of irradiation time (90 W power) and a purge time of 5 min. The HCN generated was absorbed into an accepting NaOH solution using very simple glassware apparatus that was appropriate for the microwave oven cavity. After that, the cyanide concentration was determined within 90 s using a well-known spectrophotometric flow injection analysis system. Total cyanide analysis required 15 min irradiation time (90 W power), as well as chemical conditions such as the presence of EDTA-acetate buffer solution or ascorbic acid, depending on the effluent to be analyzed (petroleum refinery or electroplating effluents, respectively). The detection limit was 0.018 mg CN l(-1) (quantification limit of 0.05 mg CN l(-1)), and the measured RSD was better than 8% for ten independent analyses of effluent samples (1.4 mg l(-1) cyanide). The accuracy of the procedure was assessed via analyte spiking (with free and complex cyanides) and by performing an independent sample analysis based on the standard methodology recommended by the APHA for comparison. The sample preparation procedure takes only 10 min for free and 20 min for total cyanide, making this procedure much faster than traditional methodologies (conventional heating and distillation), which are time-consuming (they require at least 1 h). Samples from oil (sour and stripping tower bottom waters) and electroplating effluents were analyzed successfully.

  11. Annular denuders for use in global climate and stratospheric measurements of acidic gases and particles

    NASA Technical Reports Server (NTRS)

    Stevens, Robert K.

    1991-01-01

    Measurements of acidic and basic gases that coexist with fine particle (less than 2.5 micron) may be useful for determining the impact of these species on global climate changes and determining species that influence stratospheric ozone levels. Annular denuders are well suited for this purpose. A new concentric annular denuder system, consisting of a three channel denuder, a Teflon coated cyclone preseparator, and a multistage filter pack was developed, evaluated, and shown to provide reliable atmospheric measurements of SO2, HNO2, HNO3, NH3, SO4(=), NH4(+), NO3(-), and H(+). For example, the precision of the annular denuder for the ambient measurements of HNO3 and nitrates at concentrations between 0.1 to 3 microgram/cu m was + or - 12 and 16 pct., respectively. The 120 x 25 mm three channel denuder is encased in a stainless steel sheath and has annular spaces that are 1 mm wide. This design was shown to have nearly identical capacity for removal of SO2 as conventional 210 x 25 mm single channel denuder configurations. The cyclone preseparator was designed and tested to have a D sub 50 cutoff diameter of 2.5 micron and minimal retention of HNO3.

  12. Vapor spill monitoring method

    DOEpatents

    Bianchini, Gregory M.; McRae, Thomas G.

    1985-01-01

    Method for continuous sampling of liquified natural gas effluent from a spill pipe, vaporizing the cold liquified natural gas, and feeding the vaporized gas into an infrared detector to measure the gas composition. The apparatus utilizes a probe having an inner channel for receiving samples of liquified natural gas and a surrounding water jacket through which warm water is flowed to flash vaporize the liquified natural gas.

  13. In vitro short-term bonding performance of zirconia treated with hot acid etching and primer conditioning etching and primer conditioning.

    PubMed

    Xie, Haifeng; Chen, Chen; Dai, Wenyong; Chen, Gang; Zhang, Feimin

    2013-01-01

    This study aimed to investigate and compare the resin bond strengths of zirconia conditioned as follows: alumina sandblasting; alumina sandblasting+application of 10-MDP-containing primer; alumina sandblasting+application of Z-Prime Plus or Metal/Zirconia Primer (new zirconia primers); tribochemical silica coating+silanization; hot acid etching in three different combinations [H2SO4/(NH4)2SO4, HF/HNO3, H2SO4/HF/HNO3]+application of 10-MDP-containing primer. Shear bond strengths (SBS) after water storage for 24 h and 40 days were measured to assess resin bonding performance. Surface and chemical properties of conditioned zirconia surfaces and primers were characterized using scanning electron microscopy, energy dispersive X-ray spectrometry, Fourier transform infrared spectroscopy, and atomic force microscopy. Surface roughness ranked in descending order was: hot acid etching > tribochemical silica coating > alumina sandblasting. Combination of tribochemical silica coating and silanization showed the highest initial SBS (12.46±2.13 MPa) (P<0.01). Etching with H2SO4/(NH4)2SO4 (13.15±3.24 MPa) and HF/HNO3 (13.48±2.15 MPa) showed significantly better bond durability (P<0.01). Hot acid etching seemed to be a promising surface roughening treatment to improve resin-zirconia bonding.

  14. Vapor Pressure of Methyl Salicylate and n-Hexadecane

    DTIC Science & Technology

    2014-01-01

    VAPOR PRESSURE OF METHYL SALICYLATE AND N-HEXADECANE ECBC-TR-1184 David E. Tevault Leonard C. Buettner...REPORT TYPE Final 3. DATES COVERED (From - To) Mar 2000-Dec 2001 4. TITLE AND SUBTITLE Vapor Pressure of Methyl Salicylate and n-Hexadecane 5a...ABSTRACT Vapor pressure data are reported for O-hydroxybenzoic acid, methyl ester, more commonly known as methyl salicylate (MeS), and n-hexadecane in

  15. Immobilization of EAFD heavy metals using acidic materials.

    PubMed

    Mitrakas, Manassis G; Sikalidis, Constantinos A; Karamanli, Theoktisti P

    2007-03-01

    This study was undertaken to determine the chemical and leaching characteristics of the Electric Arc Furnace Dust (EAFD) generated by a Greek plant and to investigate various acidic materials efficiency on the EAFD stabilization. In order to investigate how [OH(-)] neutralization influences EAFD heavy metals leachability, Na HCO3(-), HNO3 and H3PO4 were used as acidic materials. The concentration of Pb in leachate was found between 40 and 3.7 x 10(3) mg Pb/kg of EAFD, exceeding in all EAFD samples the maximum acceptable limit (MAL) 25 mg/kg for landfill disposal. Neutralization of [OH(-)] with HCO3(-) decreased Pb concentration in leachate at 350 mg Pb/kg of EAFD, while excess over a stoichiometry in HCO3(-) addition increased leachability of Pb, Cd, Cr, Cu as well as F. Using HNO3 as an acidic material decreased leachability of almost all the parameters concerning the EC directive 33/19-01-2003 in a pH value up to 7.2, in exception of Zn. Zinc leachability showed a U shape curve as a function of pH value. The concentration of Zn was minimized in a concentration lower than 1 mg Zn/kg EAFD in a pH range 10.5 to 9 and exceeded the MAL 90 mg/kg at a pH value 7.2. However, the major disadvantage of HNO3 was proved to be its leachability, since NO3(-) concentration in leachate was equal to HNO3 dose. H3PO4 was found the most promising acidic material for the chemical immobilization of heavy metals, since it decreased their leachability in a concentration significantly lower than MAL at a pH value up to 7.1. Finally, the concentration of Cl(-) ranged between 18 and 33 x 10(3) mg Cl(-)/kg EAFD exceeding in all EAFD samples the MAL 17 x 10(3) mg/kg. This high concentration of Cl(-) is attributed to the scrap and it could be reduced only by modification of its composition.

  16. Petroleum Vapor - Field Technical

    EPA Science Inventory

    The screening approach being developed by EPA OUST to evaluate petroleum vapor intrusion (PVI) requires information that has not be routinely collected in the past at vapor intrusion sites. What is the best way to collect this data? What are the relevant data quality issues and ...

  17. Stratospheric water vapor feedback

    PubMed Central

    Dessler, A. E.; Schoeberl, M. R.; Wang, T.; Davis, S. M.; Rosenlof, K. H.

    2013-01-01

    We show here that stratospheric water vapor variations play an important role in the evolution of our climate. This comes from analysis of observations showing that stratospheric water vapor increases with tropospheric temperature, implying the existence of a stratospheric water vapor feedback. We estimate the strength of this feedback in a chemistry–climate model to be +0.3 W/(m2⋅K), which would be a significant contributor to the overall climate sensitivity. One-third of this feedback comes from increases in water vapor entering the stratosphere through the tropical tropopause layer, with the rest coming from increases in water vapor entering through the extratropical tropopause. PMID:24082126

  18. Investigations of AlGaN/GaN HFETs utilizing post-metallization etching by nitric acid treatment

    NASA Astrophysics Data System (ADS)

    Chou, Bo-Yi; Hsu, Wei-Chou; Lee, Ching-Sung; Liu, Han-Yin; Tsai, Chih-Ming; Ho, Chiu-Sheng

    2013-07-01

    This work investigates AlGaN/GaN heterostructure field-effect transistors (HFETs) processed by using a simple post-metallization etching (PME) treatment. Decreased gate length (LG) can be achieved by using nitric acid (HNO3) PME treatment owing to the high etching selectivity of HNO3 of Ni against the Au and GaN layer. Influences on LG, etched gate profiles and device characteristics with respect to different PME processing parameters by HNO3 treatment are systematically investigated. Optimum device performance is obtained as LG was reduced to 0.5 µm by using a 1 µm long gate mask by immersing the device into a 45% diluted HNO3 solution for 35 s. Improved device performances, including maximum drain-source current density (IDS, max: 657.6 mA mm-1 → 898.5 mA mm-1), drain-source saturation current density at zero gate bias (IDSS0: 448.3 mA mm-1 → 653.4 mA mm-1), maximum extrinsic transconductance (gm, max: 158.3 mS mm-1 → 219.2 mS mm-1), unity-gain cut-off frequency (fT: 12.35 GHz → 22.05 GHz), maximum oscillation frequency (fmax: 17.55 GHz → 29.4 GHz) and power-added efficiency (P.A.E.: 26.3% → 34.5%) compared to the untreated reference device, have been successfully achieved.

  19. Evaluation of oxygen pressurized microwave-assisted digestion of botanical materials using diluted nitric acid.

    PubMed

    Bizzi, Cezar Augusto; Barin, Juliano Smanioto; Müller, Edson Irineu; Schmidt, Lucas; Nóbrega, Joaquim A; Flores, Erico Marlon Moraes

    2011-02-15

    The feasibility of diluted nitric acid solutions for microwave-assisted decomposition of botanical samples in closed vessels was evaluated. Oxygen pressurized atmosphere was used to improve the digestion efficiency and Al, Ca, K, Fe, Mg and Na were determined in digests by inductively coupled plasma optical emission spectrometry (ICP OES). Efficiency of digestion was evaluated taking into account the residual carbon content (RCC) and residual acidity in digests. Samples were digested using nitric acid solutions (2, 3, 7, and 14 mol L(-1) HNO(3)) and the effect of gas phase composition inside the reaction vessels by purging the vessel with Ar (inert atmosphere, 1 bar), air (20% of oxygen, 1 bar) and pure O(2) (100% of oxygen, 1 bar) was evaluated. The influence of oxygen pressure was studied using pressures of 5, 10, 15 and 20 bar. It was demonstrated that a diluted nitric acid solution as low as 3 mol L(-1) was suitable for an efficient digestion of sample masses up to 500 mg of botanical samples using 5 bar of oxygen pressure. The residual acidities in final digests were lower than 45% in relation to the initial amount of acid used for digestion (equivalent to 1.3 mol L(-1) HNO(3)). The accuracy of the proposed procedure was evaluated using certified reference materials of olive leaves, apple leaves, peach leaves and pine needles. Using the optimized conditions for sample digestion, the results obtained were in agreement with certified values. The limit of quantification was improved up to a factor of 14.5 times for the analytes evaluated. In addition, the proposed procedure was in agreement with the recommendations of the green chemistry once it was possible to obtain relatively high digestion efficiency (RCC<5%) using only diluted HNO(3), which is important to minimize the generation of laboratory residues.

  20. Vapor resistant arteries

    NASA Technical Reports Server (NTRS)

    Shaubach, Robert M. (Inventor); Dussinger, Peter M. (Inventor); Buchko, Matthew T. (Inventor)

    1989-01-01

    A vapor block resistant liquid artery structure for heat pipes. A solid tube artery with openings is encased in the sintered material of a heat pipe wick. The openings are limited to that side of the artery which is most remote from the heat source. The liquid in the artery can thus exit the artery through the openings and wet the sintered sheath, but vapor generated at the heat source is unlikely to move around the solid wall of the artery and reverse its direction in order to penetrate the artery through the openings. An alternate embodiment uses finer pore size wick material to resist vapor entry.

  1. Vapor generator wand

    NASA Technical Reports Server (NTRS)

    Robelen, David B. (Inventor)

    1996-01-01

    A device for producing a stream of vapor for wind tunnel airflow visualization is described. An electrically conductive heating tube is used to resistively heat a vapor producing liquid. The heating and delivery systems are integrated to allow the device to present a small cross section to the air flow, thereby reducing disturbances due to the device. The simplicity of the design allows for inexpensive implementation and construction. The design is readily scaled for use in various wind tunnel applications. The device may also find uses in manufacturing, producing a vapor for deposition on a substrate.

  2. Variational Calculations of IR Ro-Vibrational Spectra for Nitric Acid

    NASA Astrophysics Data System (ADS)

    Pavlyuchko, A. I.; Yurchenko, S. N.; Tennyson, J.

    2013-09-01

    To model the atmospheric composition of the potentially habitable planets, it is essential to have comprehensive data on the spectroscopic properties of the main molecular absorbers. This is especially true in the infrared region which is dominated by transitions of polyatomic molecules [1]. Nitric acid (HNO3) is an important constituent of the Earth atmosphere where it is a prominent bio-signature. Here we present simulations of the absorption spectra for HNO3. We have developed a variational method to solve the ro-vibrational Schrödinger equation for a general polyatomic molecule. The ro-vibrational Hamiltonian is given by [2] where the internal curvilinear vibrational coordinates qi are used to represent the displacements of the bond lengths and bond angles, ?ij(q) are elements of the matrix of the kinematic coefficients, t is the determinant of this matrix, 'a are the Euler angles, and μab(q) is the inverse matrix of the tensor of inertia. The potential energy function, V (q), is given by a fourthorder polynomial expansion in terms of Morse variables xi = 1 - e-iqi for the stretching coordinates and xi = qi for the bending coordinates. The dipole moment of the molecule is presented in the form of a Taylor series of the 2nd order in terms of qi. The parameters of the potential energy and the dipole moment functions of HNO3 were calculated by the quantum chemical method at the CCSD(T)/aug-cc-pVQZ level of theory. With this potential energy function, agreement between the calculated and experimental fundamental frequencies of vibrations is within 5 cm -1. The harmonic part of the potential function was then optimized by fitting to the experimental fundamental frequencies and used to simulate the IR spectra of HNO3. The results are in good agreement with the experimental data. The figure shows an example of the simulated spectra of HNO3 in the area of the strong Fermi resonance between the -5 and 2-9 bands along with an experimental counterpart. The resulting

  3. AMTEC vapor-vapor series connected cells

    NASA Technical Reports Server (NTRS)

    Underwood, Mark L. (Inventor); Williams, Roger M. (Inventor); Ryan, Margaret A. (Inventor); Nakamura, Barbara J. (Inventor); Oconnor, Dennis E. (Inventor)

    1995-01-01

    An alkali metal thermoelectric converter (AMTEC) having a plurality of cells structurally connected in series to form a septum dividing a plenum into two chambers, and electrically connected in series, is provided with porous metal anodes and porous metal cathodes in the cells. The cells may be planar or annular, and in either case a metal alkali vapor at a high temperature is provided to the plenum through one chamber on one side of the wall and returned to a vapor boiler after condensation at a chamber on the other side of the wall in the plenum. If the cells are annular, a heating core may be placed along the axis of the stacked cells. This arrangement of series-connected cells allows efficient generation of power at high voltage and low current.

  4. Effects of acid fog and dew on materials. Final report

    SciTech Connect

    Mansfeld, F.; Henry, R.; Vijayakumar, R.

    1989-10-01

    Field exposure tests have been carried out in order to separate the effects of acidic fog on materials damage from those caused by rain, dew and natural weathering. The test sites were McKittrick and Visalia in the Central Valley and West Casitas Pass in Ventura County. The field tests have been supported by laboratory tests in which materials damage has been determined during exposure to carefully controlled fog water chemistry. Analysis of the field exposure results for galvanized steel and the paint samples shows that the corrosivity of the atmosphere at the three test sites have been very low. The result is confirmed by the ACRM data which show very low corrosion activity. Since corrosion rates were so low approaching those for natural weathering, it was not possible to determine the effects of acidic fog. Based on the aerometric data and the observed corrosion behavior, it is doubtful that acidic fog conditions prevailed for significant times during the exposure period of 1/87 - 3/88 at Visalia and McKittrick. The results of the laboratory tests show that exposure to HNO3 at low pH and to high pollutant concentration increased the corrosion rate of galvanized steel to over 10 micro m/year. Exposure to HNO3 caused serious corrosion damage to anodized aluminum and the paint.

  5. Vapor Control Layer Recommendations

    SciTech Connect

    2009-09-08

    This information sheet describes the level of vapor control required on the interior side of framed walls with typical fibrous cavity insulation (fibreglass, rockwool, or cellulose, based on DOE climate zone of construction.

  6. Gasoline Vapor Recovery

    NASA Technical Reports Server (NTRS)

    1979-01-01

    Gasoline is volatile and some of it evaporates during storage, giving off hydrocarbon vapor. Formerly, the vapor was vented into the atmosphere but anti-pollution regulations have precluded that practice in many localities, so oil companies and storage terminals are installing systems to recover hydrocarbon vapor. Recovery provides an energy conservation bonus in that most of the vapor can be reconverted to gasoline. Two such recovery systems are shown in the accompanying photographs (mid-photo at right and in the foreground below). They are actually two models of the same system, although.configured differently because they are customized to users' needs. They were developed and are being manufactured by Edwards Engineering Corporation, Pompton Plains, New Jersey. NASA technological information proved useful in development of the equipment.

  7. Gasoline Reid Vapor Pressure

    EPA Pesticide Factsheets

    EPA regulates the vapor pressure of gasoline sold at retail stations during the summer ozone season to reduce evaporative emissions from gasoline that contribute to ground-level ozone and diminish the effects of ozone-related health problems.

  8. Effect of the acidic strength on the vapor phase Beckmann rearrangement of cyclohexanone oxime over the MFI zeolite: an embedded ONIOM study.

    PubMed

    Sirijaraensre, Jakkapan; Limtrakul, Jumras

    2009-01-21

    The mechanism and energetic profile of the Beckmann rearrangement reaction of cyclohexanone oxime to epsilon-caprolactam catalyzed by the H-[Al]-MFI and H-[B]-MFI zeolites were investigated by both the bare cluster and the ONIOM models at the B3LYP/6-31G(d,p) and the B3LYP/6-31G(d,p):MNDO levels of theory, respectively. In order to improve the energetic properties and take into account the whole zeolite framework effect, single point calculations are undertaken at the embedded ONIOM2 schemes; MP2/6-311G(d,p):HF/6-31G(d) with an additional long-range electrostatic potential from the extended zeolite framework. The reaction mechanism of the Beckmann rearrangement over the acid site of zeolites consists of three steps: the 1,2 H shift, the rearrangement and the tautomerization. The activation energies for the Beckmann rearrangement of cyclohexanone oxime on the H-[Al]-MFI zeolite are calculated to be 31.46, 16.15 and 18.95 kcal mol(-1), for the first, second and third steps, respectively, whereas in the H-[B]-MFI zeolite, the energy barriers for each step of the reaction are 24.33, 7.46 and 20.43 kcal mol(-1), respectively. The rate-determining step of the reaction is the first step, which is the transformation from the N-ended cyclohexanone oxime adsorption complex and the O-ended one. These results signify the important role that the acid strength of zeolites plays in altering the energy profile of the reaction. The results further indicate that the weak Brønsted acid sites in the [B]-MFI zeolite could better catalyze the Beckmann rearrangement of cyclohexanone oxime than the strong acid sites in the [Al]-MFI zeolite, as compared with the quantitatively low activation energy of most steps. However, the turnover reaction of the H-[B]-MFI zeolite might be delayed by the quantitatively high desorption energy of the product as compared to the adsorption energy of the reactant.

  9. Solubility and equilibrium vapor pressures of HC1 dissolved in polar stratospheric cloud materials - Ice and the trihydrate of nitric acid

    NASA Technical Reports Server (NTRS)

    Hanson, David; Mauersberger, Konrad

    1988-01-01

    Measurements of the pressure-solubility behavior of HC1 in water ice and in the nitric acid trihydrate (NAT) crystal at 200 K are reported. It was found that HC1 is about 20 times more soluble in NAT than in ice for stratospheric conditions. A relation between HC1 pressure and substrate composition based on the Gibbs-Duhem equation is developed. This relation, along with other thermodynamic data, can be used to obtain the HC1 pressure-solubility behavior at different temperatures. Implications of these results for the south polar ozone hole are discussed.

  10. Effects of inhalation of acidic compounds on pulmonary function in allergic adolescent subjects.

    PubMed Central

    Koenig, J Q; Covert, D S; Pierson, W E

    1989-01-01

    There is concern about the human health effects of inhalation of acid compounds found in urban air pollution. It was the purpose of this study to investigate three of these acid compounds, sulfur dioxide (SO2), sulfuric acid (H2SO4), and nitric acid (HNO3) in a group of allergic adolescent subjects. Subjects were exposed during rest and moderate exercise to 0.7 mumole/m3 (68 micrograms/m3) H2SO4, 4.0 mumole/m3 (0.1 ppm) SO2, or 2.0 mumole/m3 (0.05 ppm) HNO3. Pulmonary functions (FEV1, total respiratory resistance, and maximal flow) were measured before and after exposure. Preliminary analysis based on nine subjects indicates that exposure to 0.7 mumole/m3 H2SO4 alone and in combination with SO2 caused significant changes in pulmonary function, whereas exposure to air or SO2 alone did not. FEV1 decreased an average of 6% after exposure to H2SO4 alone and 4% when the aerosol was combined with SO2. The FEV1 decrease was 2% after both air and SO2 exposures. Total respiratory resistance (RT) increased 15% after the combined H2SO4 exposures, 12% after H2SO4 alone, and 7% after exposure to air. After exposures to HNO3 alone, FEV1 decreased by 4%, and RT increased by 23%. These results are preliminary; final conclusions must wait for completion of the study. PMID:2539990

  11. Influence of crustal dust and sea spray supermicron particle concentrations and acidity on inorganic NO3− aerosol during the 2013 Southern Oxidant and Aerosol Study

    DOE PAGES

    Allen, H. M.; Draper, D. C.; Ayres, B. R.; ...

    2015-09-25

    Inorganic aerosol composition was measured in the southeastern United States, a region that exhibits high aerosol mass loading during the summer, as part of the 2013 Southern Oxidant and Aerosol Study (SOAS) campaign. Measurements using a Monitor for AeRosols and GAses (MARGA) revealed two periods of high aerosol nitrate (NO3−) concentrations during the campaign. These periods of high nitrate were correlated with increased concentrations of supermicron crustal and sea spray aerosol species, particularly Na+ and Ca2+, and with a shift towards aerosol with larger (1 to 2.5 μm) diameters. We suggest this nitrate aerosol forms by multiphase reactions of HNO3more » and particles, reactions that are facilitated by transport of crustal dust and sea spray aerosol from a source within the United States. The observed high aerosol acidity prevents the formation of NH4NO3, the inorganic nitrogen species often dominant in fine-mode aerosol at higher pH. In addition, calculation of the rate of the heterogeneous uptake of HNO3 on mineral aerosol supports the conclusion that aerosol NO3− is produced primarily by this process, and is likely limited by the availability of mineral cation-containing aerosol surface area. Modeling of NO3− and HNO3 by thermodynamic equilibrium models (ISORROPIA II and E-AIM) reveals the importance of including mineral cations in the southeastern United States to accurately balance ion species and predict gas–aerosol phase partitioning.« less

  12. Quantum mechanical study of atmospheric nitrogen oxides and nitric acid: Implications on acid rain

    SciTech Connect

    Richardson, M.D.; Davey, C.A.; Evanseck, J.D.

    1996-12-31

    The energetics of the nonhydrated and monohydrated reaction NO2 + OH {r_arrow} HNO3 were studied using computational methods. Energetic and structural data were obtained using high level ab initio calculations (up to MP4 for energetics). The activation energy was calculated to be around 8 kcal/mol for the nonhydrated system, but the presence of a single water molecule completely eliminated the barrier to nitric acid formation. The hydration of this atmospheric reaction significantly stabilizes the transition structure, leading to an activation energy of about -1 kcal/mol for the reaction. This suggests that enthalpically the reactants may spontaneously form nitric acid in the lower atmosphere where water is available for catalysis, resulting in further production of acid rain.

  13. Thermochemical study of the reactions of acid-base interaction in an aqueous solution of α-aminobutyric acid

    NASA Astrophysics Data System (ADS)

    Lytkin, A. I.; Chernikov, V. V.; Krutova, O. N.; Skvortsov, I. A.; Korchagina, A. S.

    2017-01-01

    The heat effects of the interaction between a solution of α-aminobutyric acid and solutions of HNO3 and KOH are measured by means of calorimetry in different ranges of pH at 298.15 K and values of ionic strength of 0.25, 0.5, and 0.75 (KNO3). The heat effects of the stepwise dissociation of the amino acid are determined. Standard thermodynamic characteristics (Δr H 0, Δr G 0, and Δr S 0) of the reactions of acid-base interaction in aqueous solutions of α-aminobutyric acid are calculated. The connection between the thermodynamic characteristics of the dissociation of the amino acid and the structure of this compound is considered.

  14. Nitric Acid Particles in Cold Thick Ice Clouds Observed at Global Scale: Link with Lightning, Temperature, and Upper Tropospheric Water Vapor

    NASA Technical Reports Server (NTRS)

    Chepfer, H.; Minnis, P.; Dubuisson, P.; Chiriaco, M.; Sun-Mack, S.; Riviere, E. D.

    2007-01-01

    Signatures of nitric acid particles (NAP) in cold thick ice clouds have been derived from satellite observations. Most NAP are detected in the Tropics (9 to 20% of clouds with T less than 202.5 K). Higher occurrences were found in the rare mid-latitudes very cold clouds. NAP occurrence increases as cloud temperature decreases and NAP are more numerous in January than July. Comparisons of NAP and lightning distributions show that lightning is the main source of the NOx, which forms NAP in cold clouds. Qualitative comparisons of NAP with upper tropospheric humidity distributions suggest that NAP play a role in the dehydration of the upper troposphere when the tropopause is colder than 195K.

  15. Speciation in aqueous solutions of nitric acid.

    PubMed

    Hlushak, S; Simonin, J P; De Sio, S; Bernard, O; Ruas, A; Pochon, P; Jan, S; Moisy, P

    2013-02-28

    In this study, speciation in aqueous solutions of nitric acid at 25 °C was assessed in two independent ways. First, Raman experiments were carried out and interpreted in terms of free nitrate ions, ion pairs and neutral HNO(3) molecules. In parallel, a model was developed to account for the formation of these two kinds of pairs. It was based on an extension of the binding mean spherical approximation (BiMSA), or associative MSA (AMSA), in which the size and the charge of the ions in the chemical pair may differ from those of the free ions. A simultaneous fit of the osmotic coefficient and of the proportion of free ions (obtained from Raman spectroscopy experiments) led to an estimation of the speciation in nitric acid solutions. The result obtained using this procedure was compared with the estimation obtained from the Raman experiments.

  16. The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

    SciTech Connect

    Bruce J. Mincher; Stephen P. Mezyk; Gary S. Groenewold

    2016-05-01

    Abstract The group actinide/lanthanide complexing agent octylphenylcarbamoylmethyl phosphine oxide (CMPO) has been examined for its radiation stability by measuring the kinetics of its reactions with free radicals in both the aqueous and organic phases for the free and metal-complexed ligand, identifying its degradation products for both alpha and gamma irradiation, measuring the effects on solvent extraction performance, and measuring the G-values for its degradation under various conditions. This includes the G-values for CMPO in the absence of, and in contact with the acidic aqueous phase, where it is shown that the acidic aqueous phase provides radio-protection for this ligand. It was found that both solvent and metal complexation affect the kinetics of the reaction of the •NO3 radical, a product of HNO3 radiolysis, with CMPO. For example, CMPO complexed with lanthanides has a rate constant for this reaction an order of magnitude higher than for the free ligand, and the reaction for the free ligand in the organic phase is about three times faster than in the aqueous phase. In steady state radiolysis kinetics it was determined that HNO3, although not NO3- anion, provides radio-protection to CMPO, with the G-value for its degradation decreasing with increasing acidity, until it was almost completely suppressed by irradiation in contact with 5 M HNO3. The same degradation products were produced by irradiation with alpha and gamma-sources, except that the relative abundances of these products varied. For example, the product of C-C bond scission was produced only in low amounts for gamma-radiolysis, but it was an important product for samples irradiated with a He ion beam. These results are compared to the new data appearing in the literature on DGA radiolysis, since CMPO and the DGAs both contain the amide functional group.

  17. The interaction of propionic and butyric acids with ice and HNO₃-doped ice surfaces at 195-212 K.

    PubMed

    Romanias, Manolis N; Papadimitriou, Vassileios C; Papagiannakopoulos, Panos

    2014-12-04

    The interaction of propionic and butyric acids on ice and HNO3-doped ice were studied between 195 and 212 K and low concentrations, using a Knudsen flow reactor coupled with a quadrupole mass spectrometer. The initial uptake coefficients (γ0) of propionic and butyric acids on ice as a function of temperature are given by the expressions: γ0(T) = (7.30 ± 1.0) × 10(-10) exp[(3216 ± 478)/T] and γ0(T) = (6.36 ± 0.76) × 10(-11) exp[(3810 ± 434)/T], respectively; the quoted error limits are at 95% level of confidence. Similarly, γ0 of propionic acid on 1.96 wt % (A) and 7.69 wt % (B) HNO3-doped ice with temperature are given as γ(0,A)(T) = (2.89 ± 0.26) × 10(-8) exp[(2517 ± 266)/T] and γ(0,B)(T) = (2.77 ± 0.29) × 10(-7) exp[(2126 ± 206)/T], respectively. The results show that γ0 of C1 to C4 n-carboxylic acids on ice increase with the alkyl-group length, due to lateral interactions between alkyl-groups that favor a more perpendicular orientation and well packing of H-bonded monomers on ice. The high uptakes (>10(15) molecules cm(-2)) and long recovery signals indicate efficient growth of random multilayers above the first monolayer driven by significant van der Waals interactions. The heterogeneous loss of both acids on ice and HNO3-doped ice particles in dense cirrus clouds is estimated to take a few minutes, signifying rapid local heterogeneous removal by dense cirrus clouds.

  18. Vapor core propulsion reactors

    NASA Technical Reports Server (NTRS)

    Diaz, Nils J.

    1991-01-01

    Many research issues were addressed. For example, it became obvious that uranium tetrafluoride (UF4) is a most preferred fuel over uranium hexafluoride (UF6). UF4 has a very attractive vaporization point (1 atm at 1800 K). Materials compatible with UF4 were looked at, like tungsten, molybdenum, rhenium, carbon. It was found that in the molten state, UF4 and uranium attacked most everything, but in the vapor state they are not that bad. Compatible materials were identified for both the liquid and vapor states. A series of analyses were established to determine how the cavity should be designed. A series of experiments were performed to determine the properties of the fluid, including enhancement of the electrical conductivity of the system. CFD's and experimental programs are available that deal with most of the major issues.

  19. Fuel Vaporization Effects

    NASA Technical Reports Server (NTRS)

    Bosque, M. A.

    1983-01-01

    A study of the effects of fuel-air preparation characteristics on combustor performance and emissions at temperature and pressure ranges representative of actual gas turbine combustors is discussed. The effect of flameholding devices on the vaporization process and NOx formation is discussed. Flameholder blockage and geometry are some of the elements that affect the recirculation zone characteristics and subsequently alter combustion stability, emissions and performance. A water cooled combustor is used as the test rig. Preheated air and Jet A fuel are mixed at the entrance of the apparatus. A vaporization probe is used to determine percentage of vaporization and a gas sample probe to determine concentration of emissions in the exhaust gases. The experimental design is presented and experimental expected results are discussed.

  20. Venus Balloons using Water Vapor

    NASA Astrophysics Data System (ADS)

    Izutsu, N.; Yajima, N.; Honda, H.; Imamura, T.

    We propose an inflatable balloon using water vapor for the lifting gas, which is liquid in the transportation stage before entry into the high temperature atmosphere. The envelope of the balloon has an outer layer for gas barrier (a high-temperature resistant film) and an inner layer for liquid water keeping. In the descent stage using a parachute, water widely held just inside the balloon envelope can be quickly vaporized by a lot of heat flux from the surrounding high-temperature atmosphere owing to the large surface area of the balloon. As neither gas containers nor heat exchangers are necessary, we can construct a simple, lightweight and small size Venus balloon probe system. Tentative floating altitude is 35 km below the thick clouds in the Venusian atmosphere. Selection of balloon shape and material for balloon envelope are discussed in consideration of the Venusian environment such as high-temperature, high-pressure, and sulfuric acid. Balloon deployment and inflation sequence is numerically simulated. In case of the total floating mass of 10 kg at the altitude of 35 km, the volume and mass of the balloon is 1.5 cubic meters, and 3.5 kg, respectively. The shape of the balloon is chosen to be cylindrical with a small diameter. The mass of li fting gas can be determined as 4.3 kg and the remaining 2.2 kg becomes the payload mass. The mass of the total balloon system is also just 10 kg excluding the entry capsule.

  1. Vapor concentration monitor

    DOEpatents

    Bayly, John G.; Booth, Ronald J.

    1977-01-01

    An apparatus for monitoring the concentration of a vapor, such as heavy water, having at least one narrow bandwidth in its absorption spectrum, in a sample gas such as air. The air is drawn into a chamber in which the vapor content is measured by means of its radiation absorption spectrum. High sensitivity is obtained by modulating the wavelength at a relatively high frequency without changing its optical path, while high stability against zero drift is obtained by the low frequency interchange of the sample gas to be monitored and of a reference sample. The variable HDO background due to natural humidity is automatically corrected.

  2. Vapor transport mechanisms

    NASA Technical Reports Server (NTRS)

    Workman, G. L.

    1978-01-01

    The Raman scattering furnace for investigating vapor transport mechanisms was completed and checked out. Preliminary experiments demonstate that a temperature resolution of plus and minus 5 C is possible with this system operating in a backscatter mode. In the experiments presented with the GeI 4 plus excess Ge system at temperatures up to 600 C, only the GeI4 band at 150 cm superscript minus 1 was observed. Further experiments are in progress to determine if GeI2 does become the major vapor species above 440 C.

  3. Size-controlled synthesis and formation mechanism of manganese oxide OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids

    NASA Astrophysics Data System (ADS)

    Zhang, Qin; Cheng, Xiaodi; Qiu, Guohong; Liu, Fan; Feng, Xionghan

    2016-05-01

    This study presents a simplified approach for size-controlled synthesis of manganese oxide octahedral molecular sieve (OMS-2) nanowires using potassium permanganate (KMnO4) and different inorganic acids (HCl, HNO3, and H2SO4) under reflux conditions. The morphology and nanostructure of the synthesized products are characterized by X-ray diffraction, Ar adsorption, and electron microscopy analysis, in order to elucidate the controlling effects of acid concentration and type as well as the formation mechanism of OMS-2 nanowires. The concentration of inorganic acid is a crucial factor controlling the phase of the synthesized products. OMS-2 nanowires are obtained with HCl at the concentration ≥0.96 mol/L or with HNO3 and H2SO4 at the concentrations ≥0.72 mol/L. Differently, the type of inorganic acid effectively determines the particle size of OMS-2 nanowires. When the acid is changed from HCl to HNO3 and H2SO4 in the reflux system, the average length of OMS-2 declines significantly by 60-70% (1104-442 and 339 nm), with minor decreased in the average width (43-39 and 34 nm). The formation of OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids involves a two-step process, i.e., the initial formation of layered manganese oxides, and subsequent transformation to OMS-2 via a dissolution-recrystallization process under acidic conditions. The proposed reflux route provides an alternative approach for synthesizing OMS-2 nanowires as well as other porous nano-crystalline OMS materials.

  4. Formation of substrate-based gold nanocage chains through dealloying with nitric acid

    PubMed Central

    Yan, Ziren; Wu, Ying

    2015-01-01

    Summary Metal nanocages have raised great interest because of their new properties and wide applications. Here, we report on the use of galvanic replacement reactions to synthesize substrate-supported Ag–Au nanocages from silver templates electrodeposited on transparent indium tin oxide (ITO) film coated glass. The residual Ag in the composition was dealloyed with 10% nitric acid. It was found that chains of Au nanocages were formed on the substrate surface during dealloying. When the concentration of HNO3 increased to 20%, the structures of nanocages were damaged and formed crescent or semi-circular shapes. The transfer process on the substrate surface was discussed. PMID:26199839

  5. BTSC VAPOR INSTRUSION PRIMER "VAPOR INTRUSION CONSIDERATION FOR REDEVELOPMENT"

    EPA Science Inventory

    This primer is designed for brownfields stakeholders concerned about vapor intrusion, including property owners, real estate developers, and contractors performing environmental site investigations. It provides an overview of the vapor intrusion issue and how it can impact the ap...

  6. Water vapor diffusion membranes

    NASA Technical Reports Server (NTRS)

    Holland, F. F., Jr.; Smith, J. K.

    1974-01-01

    The program is reported, which was designed to define the membrane technology of the vapor diffusion water recovery process and to test this technology using commercially available or experimental membranes. One membrane was selected, on the basis of the defined technology, and was subjected to a 30-day demonstration trial.

  7. Water vapor lidar

    NASA Technical Reports Server (NTRS)

    Ellingson, R.; Mcilrath, T.; Schwemmer, G.; Wilkerson, T. D.

    1976-01-01

    The feasibility was studied of measuring atmospheric water vapor by means of a tunable lidar operated from the space shuttle. The specific method evaluated was differential absorption, a two-color method in which the atmospheric path of interest is traversed by two laser pulses. Results are reported.

  8. Large-Scale Distributions of Tropospheric Nitric, Formic, and Acetic acids Over the Westerm Pacific Basin During Wintertime

    NASA Technical Reports Server (NTRS)

    Talbot, R. W.; Dibb, J. E.; Lefer, B. L.; Scheuer, E. M.; Bradshaw, J. D.; Sandholm, S. T.; Smyth, S.; Blake, D. R.; Blake, N. J.; Sachse, G. W.; Collins, J. E.; Gregory, G. L.

    1997-01-01

    We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3 - 12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases less than 100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15 deg N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25 deg N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r(sup 2) = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r(sup 2) = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO, mixing ratios were several parts per billion by volume (ppbv), yielding relationships with 03 and N2O consistent with those previously reported for NO(y).

  9. Enthalpy of Vaporization and Vapor Pressures: An Inexpensive Apparatus

    ERIC Educational Resources Information Center

    Battino, Rubin; Dolson, David A.; Hall, Michael A.; Letcher, Trevor M.

    2007-01-01

    A simple and inexpensive method to determine the enthalpy of vaporization of liquids by measuring vapor pressure as a function of temperature is described. The vapor pressures measured with the stopcock cell were higher than the literature values and those measured with the sidearm rubber septum cell were both higher and lower than literature…

  10. Thermogravimetric study of vapor pressure of TATP synthesized without recrystallization.

    PubMed

    Mbah, Jonathan; Knott, Debra; Steward, Scott

    2014-11-01

    This study aims at characterizing the vapor pressure signatures generated by triacetone triperoxide (TATP) that was synthesized without recrystallization by thermogravimmetric analysis (TGA) for exploitation by standoff detection technologies of explosive devices. The thermal behavior of the nonrecrystallized sample was compared with reported values. Any phase change, melting point and decomposition identification were studied by differential scanning calorimeter. Vapor pressures were estimated by the Langmuir method of evaporation from an open surface in a vacuum. Vapor pressures of TATP at different temperatures were calculated using the linear logarithmic relationship obtained from benzoic acid reference standard. Sublimation of TATP was found to follow apparent zero-order kinetics and sublimes at steady rates at 298 K and above. While the enthalpy of sublimation found, 71.7 kJ mol(-1), is in agreement with reported values the vapor pressures deviated significantly. The differences in the vapor pressures behavior are attributable to the synthesis pathway chosen in this study.

  11. BioVapor Model Evaluation

    EPA Science Inventory

    General background on modeling and specifics of modeling vapor intrusion are given. Three classical model applications are described and related to the problem of petroleum vapor intrusion. These indicate the need for model calibration and uncertainty analysis. Evaluation of Bi...

  12. Metal recovery from spent hydrodesulfurization catalysts using a combined acid-leaching and electrolysis process.

    PubMed

    Lai, Yi-Chieh; Lee, Wen-Jhy; Huang, Kuo-Lin; Wu, Chung-Mou

    2008-06-15

    This study focuses on recovering valuable metals from spent hydrodesulfurization (HDS) catalysts using a combined acid-leaching and fluidized-bed electrolysis process. The electrolytic cell was equipped with a glass bead medium, an iridium oxide mesh anode, and a stainless steel plate cathode. An acid solution consisting of concentrated HNO3/H2SO4/HCl with a volume ratio of 2:1:1 was found to be better than the other tested solution (HNO3/H2SO4=1:1) to leach the metals. For the three-acid mixture, the best solid/liquid ratio and leaching time were 40 g/L and 1 h, respectively, at 70 degrees C; under this condition, the leaching yields of target metals (Mo, Ni, and V) in the 1st stage of leaching reached 90, 99, and 99%, respectively, much higher than those in the 2nd/3rd/4th stages. When this acid leachate was electrolyzed for 2 h at 2 A constant current (current density=approximately 35.7 mA/cm2), a stable cell voltage of 5 V was observed. The electrolytic recoveries of Mo, Ni, and V were approximately 15, 61, and 66%, respectively, but extending the electrolysis time from 2 to 4 h did not increase the recoveries. For this operation, the total recoveries (leaching yieldxelectrolytic recovery) of Mo, Ni, and V were approximately 14, 60, and 65%, respectively.

  13. Uptake of formic acid on thin ice films and on ice doped with nitric acid between 195 and 211 K.

    PubMed

    Romanias, Manolis N; Zogka, Antonia G; Stefanopoulos, Vassileios G; Papadimitriou, Vassileios C; Papagiannakopoulos, Panos

    2010-12-17

    The adsorption of formic acid on thin ice films and on ice doped with nitric acid (1.96, 7.69 and 53.8 wt%) is studied as a function of temperature T=195-211 K and gas concentration (0.33-10.6)×10(11) molecule cm(-3). Experiments are performed in a Knudsen flow reactor coupled with a quadrupole mass spectrometer. The initial uptake coefficients γ are strongly and inversely dependent on the ice temperature. Initial uptake is determined at low surface coverages and ranges from (0.65-3.78)×10(-3). The adsorption uptake of formic acid on pure ice films and on ice lightly doped with HNO(3) is a reversible process, and the adsorption isotherms exhibit Langmuir behaviour. N(max)(1) is (2.94±0.67)×10(14) molecule cm(-2), in good agreement with previous measurements. The temperature dependence of K(Lin) is very well represented by the expression: K(Lin)(1)=(1.43±0.32)×10(-8) exp[(4720±520)/T] cm(3) molecule(-1); the quoted uncertainty is at the 95% level of confidence and includes systematic uncertainties. Formic acid uptakes on ice films highly doped with HNO(3) (53.8 wt%) are two orders of magnitude higher than those measured on pure ice films and irreversible, thus indicating the formation of a supercooled liquid layer on the ice films upon which dissolution of formic acid occurs. Finally, the atmospheric lifetime of formic acid due to heterogeneous loss on cirrus cloud ice particles and the removal of formic acid by adsorption are estimated under conditions related to the upper troposphere.

  14. Chemical vapor deposition growth

    NASA Technical Reports Server (NTRS)

    Ruth, R. P.; Manasevit, H. M.; Kenty, J. L.; Moudy, L. A.; Simpson, W. I.; Yang, J. J.

    1976-01-01

    A chemical vapor deposition (CVD) reactor system with a vertical deposition chamber was used for the growth of Si films on glass, glass-ceramic, and polycrystalline ceramic substrates. Silicon vapor was produced by pyrolysis of SiH4 in a H2 or He carrier gas. Preliminary deposition experiments with two of the available glasses were not encouraging. Moderately encouraging results, however, were obtained with fired polycrystalline alumina substrates, which were used for Si deposition at temperatures above 1,000 C. The surfaces of both the substrates and the films were characterized by X-ray diffraction, reflection electron diffraction, scanning electron microscopy optical microscopy, and surface profilometric techniques. Several experiments were conducted to establish baseline performance data for the reactor system, including temperature distributions on the sample pedestal, effects of carrier gas flow rate on temperature and film thickness, and Si film growth rate as a function of temperature.

  15. Stratified vapor generator

    DOEpatents

    Bharathan, Desikan; Hassani, Vahab

    2008-05-20

    A stratified vapor generator (110) comprises a first heating section (H.sub.1) and a second heating section (H.sub.2). The first and second heating sections (H.sub.1, H.sub.2) are arranged so that the inlet of the second heating section (H.sub.2) is operatively associated with the outlet of the first heating section (H.sub.1). A moisture separator (126) having a vapor outlet (164) and a liquid outlet (144) is operatively associated with the outlet (124) of the second heating section (H.sub.2). A cooling section (C.sub.1) is operatively associated with the liquid outlet (144) of the moisture separator (126) and includes an outlet that is operatively associated with the inlet of the second heating section (H.sub.2).

  16. Filter vapor trap

    DOEpatents

    Guon, Jerold

    1976-04-13

    A sintered filter trap is adapted for insertion in a gas stream of sodium vapor to condense and deposit sodium thereon. The filter is heated and operated above the melting temperature of sodium, resulting in a more efficient means to remove sodium particulates from the effluent inert gas emanating from the surface of a liquid sodium pool. Preferably the filter leaves are precoated with a natrophobic coating such as tetracosane.

  17. Copper Vapor Generator

    DTIC Science & Technology

    1974-09-01

    percent measured during this program in a static copper vapor apparatus developed at PIB . This efficiency has been calculated by dividing the energy of a... laser medium. A measure of beam quality may be defined in terms ot the energy delivered in the tar field in relatum to the energy delivered by a...phase of the work the homogeneity requirements for the medium of a high -power laser was reviewed. These requirements were translated into measurable

  18. Water vaporization on Ceres

    NASA Technical Reports Server (NTRS)

    A'Hearn, Michael F.; Feldman, Paul D.

    1992-01-01

    A search is presently conducted for OH generated by the photodissociation of atmospheric water vapor in long-exposure IUE spectra of the region around Ceres. A statistically significant detection of OH is noted in an exposure off the northern limb of Ceres after perihelion. The amount of OH is consistent with a polar cap that might be replenished during winter by subsurface percolation, but which dissipates in summer.

  19. The vapor pressures of explosives

    SciTech Connect

    Ewing, Robert G.; Waltman, Melanie J.; Atkinson, David A.; Grate, Jay W.; Hotchkiss, Peter

    2013-01-05

    The vapor pressures of many explosive compounds are extremely low and thus determining accurate values proves difficult. Many researchers, using a variety of methods, have measured and reported the vapor pressures of explosives compounds at single temperatures, or as a function of temperature using vapor pressure equations. There are large variations in reported vapor pressures for many of these compounds, and some errors exist within individual papers. This article provides a review of explosive vapor pressures and describes the methods used to determine them. We have compiled primary vapor pressure relationships traceable to the original citations and include the temperature ranges for which they have been determined. Corrected values are reported as needed and described in the text. In addition, after critically examining the available data, we calculate and tabulate vapor pressures at 25 °C.

  20. VAPOR PRESSURES AND HEATS OF VAPORIZATION OF PRIMARY COAL TARS

    SciTech Connect

    Eric M. Suuberg; Vahur Oja

    1997-07-01

    This project had as its main focus the determination of vapor pressures of coal pyrolysis tars. It involved performing measurements of these vapor pressures and from them, developing vapor pressure correlations suitable for use in advanced pyrolysis models (those models which explicitly account for mass transport limitations). This report is divided into five main chapters. Each chapter is a relatively stand-alone section. Chapter A reviews the general nature of coal tars and gives a summary of existing vapor pressure correlations for coal tars and model compounds. Chapter B summarizes the main experimental approaches for coal tar preparation and characterization which have been used throughout the project. Chapter C is concerned with the selection of the model compounds for coal pyrolysis tars and reviews the data available to us on the vapor pressures of high boiling point aromatic compounds. This chapter also deals with the question of identifying factors that govern the vapor pressures of coal tar model materials and their mixtures. Chapter D covers the vapor pressures and heats of vaporization of primary cellulose tars. Chapter E discusses the results of the main focus of this study. In summary, this work provides improved understanding of the volatility of coal and cellulose pyrolysis tars. It has resulted in new experimentally verified vapor pressure correlations for use in pyrolysis models. Further research on this topic should aim at developing general vapor pressure correlations for all coal tars, based on their molecular weight together with certain specific chemical characteristics i.e. hydroxyl group content.

  1. WACCM-D—Improved modeling of nitric acid and active chlorine during energetic particle precipitation

    NASA Astrophysics Data System (ADS)

    Andersson, M. E.; Verronen, P. T.; Marsh, D. R.; Päivärinta, S.-M.; Plane, J. M. C.

    2016-09-01

    Observations have shown that a number of neutral minor species are affected by energetic particle precipitation (EPP) and ion chemistry (IC) in the polar regions. However, to date the complexity of the ion chemistry below the mesopause (i.e., in the D region ionosphere) has restricted global models to simplified EEP/IC parameterizations which are unable to reproduce some important effects, e.g., the increase of mesospheric nitric acid (HNO3). Here we use WACCM-D, a variant of the Whole Atmosphere Community Climate Model which includes a selected set of D region ion chemistry designed to produce the observed effects of EPP/IC. We evaluate the performance of EPP/IC modeling by comparing WACCM-D results for the January 2005 solar proton event (SPE) to those from the standard WACCM and Aura/Microwave Limb Sounder (MLS) and SCISAT/Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) observations. The results indicate that WACCM-D improves the modeling of HNO3, HCl, ClO, OH, and NOx during the SPE. Northern Hemispheric HNO3 from WACCM-D shows an increase by 2 orders of magnitude at 40-70 km compared to WACCM, reaching 2.6 ppbv, in agreement with the observations. For HCl and ClO, the improvement is most pronounced in the Southern Hemisphere at 40-50 km where WACCM-D predicts a decrease of HCl and increase of ClO by 1.6% and 10%, respectively, similar to MLS data. Compared to WACCM, WACCM-D produces 25-50% less OH and 30-130% more NOx at 70-85 km which leads to better agreement with the observations. Although not addressed here, longer-term NOx impact of ion chemistry could be important for polar stratospheric ozone and middle atmospheric dynamics.

  2. Mercury determination in non- and biodegradable materials by cold vapor capacitively coupled plasma microtorch atomic emission spectrometry.

    PubMed

    Frentiu, Tiberiu; Mihaltan, Alin I; Ponta, Michaela; Darvasi, Eugen; Frentiu, Maria; Cordos, Emil

    2011-10-15

    A new analytical system consisting of a low power capacitively coupled plasma microtorch (20 W, 13.56 MHz, 150 ml min(-1) Ar) and a microspectrometer was investigated for the Hg determination in non- and biodegradable materials by cold-vapor generation, using SnCl(2) reductant, and atomic emission spectrometry. The investigated miniaturized system was used for Hg determination in recyclable plastics from electronic equipments and biodegradable materials (shopping bags of 98% biodegradable polyethylene and corn starch) with the advantages of easy operation and low analysis costs. Samples were mineralized in HNO(3)-H(2)SO(4) mixture in a high-pressure microwave system. The detection limits of 0.05 ng ml(-1) or 0.08 μg g(-1) in solid sample were compared with those reported for other analytical systems. The method precision was 1.5-9.4% for Hg levels of 1.37-13.9 mg kg(-1), while recovery in two polyethylene certified reference materials in the range 98.7 ± 4.5% (95% confidence level).

  3. Proton transfer reactions between nitric acid and acetone, hydroxyacetone, acetaldehyde and benzaldehyde in the solid phase.

    PubMed

    Lasne, Jérôme; Laffon, Carine; Parent, Philippe

    2012-12-05

    The heterogeneous and homogeneous reactions of acetone, hydroxyacetone, acetaldehyde and benzaldehyde with solid nitric acid (HNO(3)) films have been studied with Reflection-Absorption Infrared Spectroscopy (RAIRS) under Ultra-High Vacuum (UHV) conditions in the 90-170 K temperature range. In the bulk or at the surface of the films, nitric acid transfers its proton to the carbonyl function of the organic molecules, producing protonated acetone-H(+), hydroxyacetone-H(+), acetaldehyde-H(+) and benzaldehyde-H(+), and nitrate anions NO(3)(-), a reaction not observed when nitric acid is previously hydrated [J. Lasne, C. Laffon and Ph. Parent, Phys. Chem. Chem. Phys., 2012, 14, 697]. This provides a molecular-scale description of the carbonyl protonation reaction in an acid medium, the first step of the acid-catalyzed condensation of carbonyl compounds, fuelling the growth of secondary organic aerosols (SOA) in the atmosphere.

  4. The decrease in Greenland ice-core δ15N of nitrate in the industrial period: influenced by changes in atmospheric acidity?

    NASA Astrophysics Data System (ADS)

    Geng, L.; Cole-Dai, J.; Alexander, B.; Steig, E. J.; Schauer, A. J.; Savarino, J.

    2012-12-01

    Previous study in a central Greenland ice core has revealed a decreasing trend in δ15N of nitrate (δ15N (nitrate)) starting as early as 1850 C.E.. Lake sediment cores from North America show a similar trend in δ15N of total nitrogen starting around 1895 C.E.. The decrease in δ15N has been proposed to be due to the increasing deposition of anthropogenically derived (i.e., fossil fuel combustion) nitrate in the industrial period. However, this interpretation is questioned by measurements of δ15N in NOx and atmospheric nitrate. Here, we present new, annually-resolved records of δ15N (nitrate) and major ion concentrations (Cl-, NO3-, SO42-, Na+, NH4+, K+, Mg2+, and Ca2+) obtained from two central Greenland ice cores. The results (Figure 1) indicate that the significant decrease in δ15N is coincident with an increase in acidity (H+ concentration estimated based on ionic balance) beginning around 1895 C.E., which is about 50 years earlier than the start of the increase in nitrate concentration (~1945 C.E.) . This observation suggests that it is likely the acidity change, instead of the input of anthropogenic nitrate, triggered the decrease in ice-core δ15N (nitrate). Atmospheric aerosol acidity influences the partitioning of atmospheric nitrate between its gaseous (HNO3) and particulate (p-NO3-) phases, resulting in a depletion of δ15N in HNO3 relative to p-NO3-. If atmospheric nitrate is transported to central Greenland preferentially in its gaseous form (HNO3), which is an open question, a decrease in ice-core δ15N (nitrate) would be expected with an increase in atmospheric acidity. We will examine the relationships between δ15N (nitrate) and the ice-core records of acidity, and HNO3, to discern the processes from changes in atmospheric acidity to the observed variability in ice core δ15N (nitrate) during the Industrial era.igure 1. The annual NO3- (blue curve), H+ (black curve) concentrations, and annual δ15N (nitrate) (red curve, y-axis is reversely

  5. The toxicity of inhaled methanol vapors

    SciTech Connect

    Kavet, R.; Nauss, K.M. )

    1990-01-01

    Methanol could become a major automotive fuel in the U.S., and its use may result in increased exposure of the public to methanol vapor. Nearly all of the available information on methanol toxicity in humans relates to the consequences of acute, rather than chronic, exposures. Acute methanol toxicity evolves in a well-understood pattern and consists of an uncompensated metabolic acidosis with superimposed toxicity to the visual system. The toxic properties of methanol are rooted in the factors that govern both the conversion of methanol to formic acid and the subsequent metabolism of formate to carbon dioxide in the folate pathway. In short, the toxic syndrome sets in if formate generation continues at a rate that exceeds its rate of metabolism. Current evidence indicates that formate accumulation will not challenge the metabolic capacity of the folate pathway at the anticipated levels of exposure to automotive methanol vapor.117 references.

  6. Chemical Vapor Deposited Diamond

    DTIC Science & Technology

    1991-09-27

    surface roughness. 0.9 0.8 p0.7 0.6 0.5 C0.4 0.3 0.2- 0.1- 0-. 0 50 100 150 200 250 300 350 frequency (cm-1) Figure 10. Transmission spectrum of CVD...significantly less than one micrometer. The resultant films show root-mean- squared surface roughnesses -0.02 pm as long as the film thickness is not much... Derjaguin , B.V., Vapor Growth of Diamond on Diamond and Other Surfaces , J. Cryst. Growth 52:219-226 (1981); Spitsyn, B.V., The State of the Art in

  7. Vapor Pressure of GB

    DTIC Science & Technology

    2009-04-01

    EDGEWOOD CHEMICAL BIOLOGICAL CENTER U.S. ARMY RESEARCH, DEVELOPMENT AND ENGINEERING COMMAND ECBC-TR-686 VAPOR PRESSURE OF GB James H. Buchanan...275 °C under a flow rate of 20 seem UHP -grade helium for 5 min and transferred to the ACEM 900 tenax focusing trap maintained at 40 °C. Transfer...a flow rate of 8.0 seem UHP grade helium for 5 min to affect sample transfer to the gas chromatographic column. The 15 m x 0.53 mm i.d. fused silica

  8. Hydrazine-Vapor Samplers

    NASA Technical Reports Server (NTRS)

    Young, Rebecca; Mcbrearty, Charles; Curran, Dan; Leavitt, Nilgun

    1994-01-01

    Active sampling unit capable of detecting hydrazine and monomethyl hydrazine vapors at levels as low as 10 ppb in air developed. Includes detachable badge holder and pump which draws air through badge holder at selectable rate of 1 or 2 L/min. Coated strip in each badge designed to align with air passage in badge holder. Two types of badge holders constructed: one has open-face design for general monitoring of air in open spaces, while other has closed-face design with viewing window and intended for sampling through small openings to detect leaks.

  9. Aircraft measurements of ammonia and nitric acid in the lower troposphere

    NASA Astrophysics Data System (ADS)

    Lebel, P. J.; Hoell, J. M.; Levine, J. S.; Vay, S. A.

    1985-06-01

    The first simultaneous measurements of ammonia and nitric acid in the troposphere have been made from an aircraft using a tungsten oxide denuder system. Vertical profiles of NH3 and HNO3 taken over coastal Virginia and Maryland in March and September, 1983, at altitudes from 150 m to 3000 m, show mixing ratios that decrease with altitude. Ammonia profiles show substantial seasonal variation, while nitric acid profiles do not. Using the measured profiles and a one-dimensional photochemical model, lifetimes due to heterogeneous loss of one day for HNO3 and ten days for NH3 are calculated. In contrast, NH3 profiles up to 5300 m over the North Atlantic Ocean during August 1982 show mixing ratios that increase slightly with altitude. These data represent the first ammonia profiles measured over the ocean. It is suggested that the increase in NH3 with altitude is a result of an ammonia-rich continental air mass advected over the ocean, followed by the dissolution of NH3 in the marine boundary layer on water-covered sea salt particles.

  10. Vapor spill pipe monitor

    DOEpatents

    Bianchini, G.M.; McRae, T.G.

    1983-06-23

    The invention is a method and apparatus for continually monitoring the composition of liquefied natural gas flowing from a spill pipe during a spill test by continually removing a sample of the LNG by means of a probe, gasifying the LNG in the probe, and sending the vaporized LNG to a remote ir gas detector for analysis. The probe comprises three spaced concentric tubes surrounded by a water jacket which communicates with a flow channel defined between the inner and middle, and middle and outer tubes. The inner tube is connected to a pump for providing suction, and the probe is positioned in the LNG flow below the spill pipe with the tip oriented partly downward so that LNG is continuously drawn into the inner tube through a small orifice. The probe is made of a high thermal conductivity metal. Hot water is flowed through the water jacket and through the flow channel between the three tubes to provide the necessary heat transfer to flash vaporize the LNG passing through the inner channel of the probe. The gasified LNG is transported through a connected hose or tubing extending from the probe to a remote ir sensor which measures the gas composition.

  11. Effects of acid on the microstructures and properties of three-dimensional TiO2 hierarchical structures by solvothermal method.

    PubMed

    Zhou, Jing; Song, Bin; Zhao, Gaoling; Han, Gaorong

    2012-04-13

    Three-dimensional (3D) TiO2 hierarchical structures with various microstructures have been successfully synthesized via a surfactant-free and single-step solvothermal route, in which hydrochloric acid (HCl), nitric acid (HNO3), and acetic acid (HAc) are employed as the acid medium, respectively. The effects of acid medium on the microstructures and properties of 3D TiO2 hierarchical structure have been studied. The results indicate that 3D dandelion-like microspheres assembled of radial rutile nanorods are obtained in the sample prepared with HCl. Both the fraction of rutile and the diameter of nanorod enhance with the increasing HCl concentration. For the products derived from either HNO3 or HAc, 3D spheres composed of anatase nanoparticles are present. The 3D dandelion-like TiO2 hierarchical structures show low reflectance and efficient light harvesting since this ordered rod geometry offers a light-transfer path for incident light as well as multiple reflective and scattering effects. Moreover, 3D TiO2 with this unique topology shows superior photocatalytic activity despite low surface area, which can be ascribed to the enhanced light harvesting, fast electron transport, and low electron/hole recombination loss.

  12. Effects of acid on the microstructures and properties of three-dimensional TiO2 hierarchical structures by solvothermal method

    PubMed Central

    2012-01-01

    Three-dimensional (3D) TiO2 hierarchical structures with various microstructures have been successfully synthesized via a surfactant-free and single-step solvothermal route, in which hydrochloric acid (HCl), nitric acid (HNO3), and acetic acid (HAc) are employed as the acid medium, respectively. The effects of acid medium on the microstructures and properties of 3D TiO2 hierarchical structure have been studied. The results indicate that 3D dandelion-like microspheres assembled of radial rutile nanorods are obtained in the sample prepared with HCl. Both the fraction of rutile and the diameter of nanorod enhance with the increasing HCl concentration. For the products derived from either HNO3 or HAc, 3D spheres composed of anatase nanoparticles are present. The 3D dandelion-like TiO2 hierarchical structures show low reflectance and efficient light harvesting since this ordered rod geometry offers a light-transfer path for incident light as well as multiple reflective and scattering effects. Moreover, 3D TiO2 with this unique topology shows superior photocatalytic activity despite low surface area, which can be ascribed to the enhanced light harvesting, fast electron transport, and low electron/hole recombination loss. PMID:22500985

  13. The effect of the Mt. Pinatubo aerosol on the NHO3 column over Mauna Loa, Hawaii

    NASA Technical Reports Server (NTRS)

    David, Shelle J.; Murcray, Frank J.; Goldman, Aaron; Rinsland, Curtis P.; Murcray, David G.

    1994-01-01

    A very high resolution infrared solar spectrometer system for the Network for Detection of Stratospheric Change has been routinely operated at the Mauna Loa Observatory in Hawaii since November, 1991. Solar absorption spectra are normally taken one day a week at sunrise. We report the analysis of these spectra for the vertical column amount of nitric acid (HNO3) vapor. The observations began four months after the arrival of volcanic aerosols from Mt. Pinatubo over the site. Although quite variable, total HNO3 columns were initially about 7 x 10(exp 15) molecules/sq cm and have decreased about 30% in the following two years.

  14. [Determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS].

    PubMed

    Hu, Zhao-chu; Gao, Shan; Liu, Xiao-ming; Yuan, Hong-lin; Liu, Ye; Diwu, Chun-rong

    2007-12-01

    The authors studied in detail the memory effect of Bi, Sb, As and Te in ICP-MS. The produced memory effects of these element were in the order of Bi>Sb>Te>As. Bi was seriously adsorbed by the polypropylene sample storing bottle and the sample introduction system in the low nitric acid medium (0.01%-1% HNO3). The washout effect of 0.1% HF was found to be better than those of 6% HNO3 and 0.1% HClO4. Under the given experiment conditions, the instrumental limit of detection was 0.001 and 0.0001 ng x mL(-1) for Sb and Bi, respectively. The authors report the determination of Sb and Bi in 24 international geological reference materials by using pressurized acid digestion-ICP-MS (including AGV-2, BHVO-2, BCR-2, etc.). Most of the results were found to be in reasonable agreement with the reported values in the literature. The authors' determined values of Sb for GSR-1 (granite; 0.30 microg x g(-1)) and JP-1 (peridotite; 0.045 microg x g(-1)) are obviously higher than those reported values. This is attributed to the efficient pressurized acid digestion, which is generally much more efficient than conventional wet digestions for insoluble minerals.

  15. Interannual variations of early winter Antarctic polar stratospheric cloud formation and nitric acid observed by CALIOP and MLS

    NASA Astrophysics Data System (ADS)

    Lambert, Alyn; Santee, Michelle L.; Livesey, Nathaniel J.

    2016-12-01

    We use satellite-borne measurements collected over the last decade (2006-2015) from the Aura Microwave Limb Sounder (MLS) and the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) to investigate the nitric acid distribution and the properties of polar stratospheric clouds (PSCs) in the early winter Antarctic vortex. Frequently, at the very start of the winter, we find that synoptic-scale depletion of HNO3 can be detected in the inner vortex before the first lidar detection of geophysically associated PSCs. The generation of "sub-visible" PSCs can be explained as arising from the development of a solid particle population with low number densities and large particle sizes. Assumed to be composed of nitric acid trihydrate (NAT), the sub-visible PSCs form at ambient temperatures well above the ice frost point, but also above the temperature at which supercooled ternary solution (STS) grows out of the background supercooled binary solution (SBS) distribution. The temperature regime of their formation, inferred from the simultaneous uptake of ambient HNO3 into NAT and their Lagrangian temperature histories, is at a depression of a few kelvin with respect to the NAT existence threshold, TNAT. Therefore, their nucleation requires a considerable supersaturation of HNO3 over NAT, and is consistent with a recently described heterogeneous nucleation process on solid foreign nuclei immersed in liquid aerosol. We make a detailed investigation of the comparative limits of detection of PSCs and the resulting sequestration of HNO3 imposed by lidar, mid-infrared, and microwave techniques. We find that the temperature history of air parcels, in addition to the local ambient temperature, is an important factor in the relative frequency of formation of liquid/solid PSCs. We conclude that the initiation of NAT nucleation and the subsequent development of large NAT particles capable of sedimentation and denitrification in the early winter do not emanate from an ice

  16. Iron bromide vapor laser

    NASA Astrophysics Data System (ADS)

    Sukhanov, V. B.; Shiyanov, D. V.; Trigub, M. V.; Dimaki, V. A.; Evtushenko, G. S.

    2016-03-01

    We have studied the characteristics of a pulsed gas-discharge laser on iron bromide vapor generating radiation with a wavelength of 452.9 nm at a pulse repetition frequency (PRF) of 5-30 kHz. The maximum output power amounted to 10 mW at a PRF within 5-15 kHz for a voltage of 20-25 kV applied to electrodes of the discharge tube. Addition of HBr to the medium produced leveling of the radial profile of emission. Initial weak lasing at a wavelength of 868.9 nm was observed for the first time, which ceased with buildup of the main 452.9-nm line.

  17. Chemical vapor deposition growth

    NASA Technical Reports Server (NTRS)

    Ruth, R. P.; Manasevit, H. M.; Kenty, J. L.; Moudy, L. A.; Simpson, W. I.; Yang, J. J.

    1976-01-01

    The chemical vapor deposition (CVD) method for the growth of Si sheet on inexpensive substrate materials is investigated. The objective is to develop CVD techniques for producing large areas of Si sheet on inexpensive substrate materials, with sheet properties suitable for fabricating solar cells meeting the technical goals of the Low Cost Silicon Solar Array Project. Specific areas covered include: (1) modification and test of existing CVD reactor system; (2) identification and/or development of suitable inexpensive substrate materials; (3) experimental investigation of CVD process parameters using various candidate substrate materials; (4) preparation of Si sheet samples for various special studies, including solar cell fabrication; (5) evaluation of the properties of the Si sheet material produced by the CVD process; and (6) fabrication and evaluation of experimental solar cell structures, using standard and near-standard processing techniques.

  18. Vapor compression distillation module

    NASA Technical Reports Server (NTRS)

    Nuccio, P. P.

    1975-01-01

    A Vapor Compression Distillation (VCD) module was developed and evaluated as part of a Space Station Prototype (SSP) environmental control and life support system. The VCD module includes the waste tankage, pumps, post-treatment cells, automatic controls and fault detection instrumentation. Development problems were encountered with two components: the liquid pumps, and the waste tank and quantity gauge. Peristaltic pumps were selected instead of gear pumps, and a sub-program of materials and design optimization was undertaken leading to a projected life greater than 10,000 hours of continuous operation. A bladder tank was designed and built to contain the waste liquids and deliver it to the processor. A detrimental pressure pattern imposed upon the bladder by a force-operated quantity gauge was corrected by rearranging the force application, and design goals were achieved. System testing has demonstrated that all performance goals have been fulfilled.

  19. THERMALLY OPERATED VAPOR VALVE

    DOEpatents

    Dorward, J.G. Jr.

    1959-02-10

    A valve is presented for use in a calutron to supply and control the vapor to be ionized. The invention provides a means readily operable from the exterior of the vacuum tank of the apparatuss without mechanical transmission of forces for the quick and accurate control of the ionizing arc by a corresponding control of gas flow theretos thereby producing an effective way of carefully regulating the operation of the calutron. The invention consists essentially of a tube member extending into the charge bottle of a calutron devices having a poppet type valve closing the lower end of the tube. An electrical heating means is provided in the valve stem to thermally vary the length of the stem to regulate the valve opening to control the flow of material from the charge bottle.

  20. Solvents and vapor intrusion pathways.

    PubMed

    Phillips, Scott D; Krieger, Gary R; Palmer, Robert B; Waksman, Javier C

    2004-08-01

    Vapor intrusion must be recognized appropriately as a separate pathway of contamination. Although many issues resemble those of other forms of contamination (particularly its entryway, which is similar to that of radon seepage), vapor intrusion stands apart as a unique risk requiring case-specific action. This article addresses these issues and the current understanding of the most appropriate and successful remedial actions.

  1. Student Exposure to Mercury Vapors.

    ERIC Educational Resources Information Center

    Weber, Joyce

    1986-01-01

    Discusses the problem of mercury vapors caused by spills in high school and college laboratories. Describes a study which compared the mercury vapor levels of laboratories in both an older and a newer building. Concludes that the mercurial contamination of chemistry laboratories presents minimal risks to the students. (TW)

  2. Constrained Vapor Bubble

    NASA Technical Reports Server (NTRS)

    Huang, J.; Karthikeyan, M.; Plawsky, J.; Wayner, P. C., Jr.

    1999-01-01

    The nonisothermal Constrained Vapor Bubble, CVB, is being studied to enhance the understanding of passive systems controlled by interfacial phenomena. The study is multifaceted: 1) it is a basic scientific study in interfacial phenomena, fluid physics and thermodynamics; 2) it is a basic study in thermal transport; and 3) it is a study of a heat exchanger. The research is synergistic in that CVB research requires a microgravity environment and the space program needs thermal control systems like the CVB. Ground based studies are being done as a precursor to flight experiment. The results demonstrate that experimental techniques for the direct measurement of the fundamental operating parameters (temperature, pressure, and interfacial curvature fields) have been developed. Fluid flow and change-of-phase heat transfer are a function of the temperature field and the vapor bubble shape, which can be measured using an Image Analyzing Interferometer. The CVB for a microgravity environment, has various thin film regions that are of both basic and applied interest. Generically, a CVB is formed by underfilling an evacuated enclosure with a liquid. Classification depends on shape and Bond number. The specific CVB discussed herein was formed in a fused silica cell with inside dimensions of 3x3x40 mm and, therefore, can be viewed as a large version of a micro heat pipe. Since the dimensions are relatively large for a passive system, most of the liquid flow occurs under a small capillary pressure difference. Therefore, we can classify the discussed system as a low capillary pressure system. The studies discussed herein were done in a 1-g environment (Bond Number = 3.6) to obtain experience to design a microgravity experiment for a future NASA flight where low capillary pressure systems should prove more useful. The flight experiment is tentatively scheduled for the year 2000. The SCR was passed on September 16, 1997. The RDR is tentatively scheduled for October, 1998.

  3. Vapor phase heat transport systems

    NASA Astrophysics Data System (ADS)

    Hedstrom, J. C.; Neeper, D. A.

    1985-09-01

    Progress in theoretical and experimental investigations of various forms of a vapor transport system for solar space heating is described, which could also be applied to service water heating. The refrigerant is evaporated in a solar collector, which may be located on the external wall or roof of a building. The vapor is condensed in a passively discharged thermal storage unit located within the building. The condensed liquid can be returned to the collector either by a motor-driven pump or by a completely passive self-pumping mechanism in which the vapor pressure lifts the liquid from the condenser to the collector. The theoretical investigation analyzes this self-pumping scheme. Experiments in solar test cells compared the operation of both passive and active forms of the vapor system with the operation of a passive water wall. The vapor system operates as expected, with potential advantages over other passive systems in design flexibility and energy yield.

  4. SOFIA Water Vapor Monitor Design

    NASA Technical Reports Server (NTRS)

    Cooper, R.; Roellig, T. L.; Yuen, L.; Shiroyama, B.; Meyer, A.; Devincenzi, D. (Technical Monitor)

    2002-01-01

    The SOFIA Water Vapor Monitor (WVM) is a heterodyne radiometer designed to determine the integrated amount of water vapor along the telescope line of sight and directly to the zenith. The basic technique that was chosen for the WVM uses radiometric measurements of the center and wings of the 183.3 GHz rotational line of water to measure the water vapor. The WVM reports its measured water vapor levels to the aircraft Mission Controls and Communication System (MCCS) while the SOFIA observatory is in normal operation at flight altitude. The water vapor measurements are also available to other scientific instruments aboard the observatory. The electrical, mechanical and software design of the WVM are discussed.

  5. A Lithium Vapor Box similarity experiment employing water vapor

    NASA Astrophysics Data System (ADS)

    Schwartz, Ja; Jagoe, C.; Goldston, Rj; Jaworski, Ma

    2016-10-01

    Handling high power loads and heat flux in the divertor is a major challenge for fusion power plants. A detached plasma will likely be required. However, hydrogenic and impurity puffing experiments show that detached operation leads easily to X-point MARFEs, impure plasmas, degradation in confinement, and lower helium pressure at the exhaust. The concept of the Lithium Vapor Box Divertor is to use local evaporation and strong differential pumping through condensation to localize the gas-phase material that absorbs the plasma heat flux, and so avoid those difficulties. In order to design such a box first the vapor without plasma must be simulated. The density of vapor required can be estimated using the SOL power, major radius, poloidal box length, and cooling energy per lithium atom. For an NSTX-U-sized machine, the Knudsen number Kn spans 0.01 to 1, the transitional flow regime. This regime cannot handled by fluid codes or collisionless Monte Carlo codes, but can be handled by Direct Simulation Monte Carlo (DSMC) codes. To validate a DSMC model, we plan to build a vapor box test stand employing more-convenient water vapor instead of lithium vapor as the working fluid. Transport of vapor between the chambers at -50C will be measured and compared to the model. This work supported by DOE Contract No. DE-AC02-09CH11466.

  6. Vapor pressure measured with inflatable plastic bag

    NASA Technical Reports Server (NTRS)

    1965-01-01

    Deflated plastic bag in a vacuum chamber measures initial low vapor pressures of materials. The bag captures the test sample vapors and visual observation of the vapor-inflated bag under increasing external pressures yields pertinent data.

  7. A Citizen's Guide to Vapor Intrusion Mitigation

    EPA Pesticide Factsheets

    This guide describes how vapor intrusion is the movement of chemical vapors from contaminated soil and groundwater into nearby buildings.Vapors primarily enter through openings in the building foundation or basement walls.

  8. Tested Demonstrations. Gasoline Vapor: An Invisible Pollutant

    ERIC Educational Resources Information Center

    Stephens, Edgar R.

    1977-01-01

    Describes a demonstration concerning the air pollution aspects of gasoline vapor which provides an estimation of the vapor pressure of test fuel, the molecular weight of the vapor, and illustrates a method of controlling the pollution. (SL)

  9. Effects of acid pre-treatment on bio-hydrogen production and microbial communities during dark fermentation.

    PubMed

    Lee, Myoung-Joo; Song, Ji-Hyeon; Hwang, Sun-Jin

    2009-02-01

    Optimal conditions for acid pre-treatment were investigated for the enrichment of hydrogen-producing bacteria (HPB) in a mixed culture using three strong acids: HCl, HNO(3), and H2SO4 x HCl was selected as a suitable acid for the enrichment of HPB in the fermentation process. The volume of bio-hydrogen produced when the mixed culture was pre-treated using HCl at pH 2 was 3.2 times higher than that obtained without acid pre-treatment. Changes in the microbial community during acid pre-treatment were monitored using images obtained by the fluorescent in situ hybridization (FISH) method and the Live/Dead cell viability test. The tests clearly indicated that the Clostridium species of cluster I were the predominant strains involved in bio-H(2) fermentation, and could be selectively enriched by HCl pre-treatment.

  10. Vapor Pressure, Vapor Composition and Fractional Vaporization of High Temperature Lavas on Io

    NASA Technical Reports Server (NTRS)

    Fegley, B., Jr.; Schaefer, L.; Kargel, J. S.

    2003-01-01

    Observations show that Io's atmosphere is dominated by SO2 and other sulfur and sulfur oxide species, with minor amounts of Na, K, and Cl gases. Theoretical modeling and recent observations show that NaCl, which is produced volcanically, is a constituent of the atmosphere. Recent Galileo, HST and ground-based observations show that some volcanic hot spots on Io have extremely high temperatures, in the range 1400-1900 K. At similar temperatures in laboratory experiments, molten silicates and oxides have significant vapor pressures of Na, K, SiO, Fe, Mg, and other gases. Thus vaporization of these species from high temperature lavas on Io seems likely. We therefore modeled the vaporization of silicate and oxide lavas suggested for Io. Our results for vapor chemistry are reported here. The effects of fractional vaporization on lava chemistry are given in a companion abstract by Kargel et al.

  11. Passive vapor extraction feasibility study

    SciTech Connect

    Rohay, V.J.

    1994-06-30

    Demonstration of a passive vapor extraction remediation system is planned for sites in the 200 West Area used in the past for the disposal of waste liquids containing carbon tetrachloride. The passive vapor extraction units will consist of a 4-in.-diameter pipe, a check valve, a canister filled with granular activated carbon, and a wind turbine. The check valve will prevent inflow of air that otherwise would dilute the soil gas and make its subsequent extraction less efficient. The granular activated carbon is used to adsorb the carbon tetrachloride from the air. The wind turbine enhances extraction rates on windy days. Passive vapor extraction units will be designed and operated to meet all applicable or relevant and appropriate requirements. Based on a cost analysis, passive vapor extraction was found to be a cost-effective method for remediation of soils containing lower concentrations of volatile contaminants. Passive vapor extraction used on wells that average 10-stdft{sup 3}/min air flow rates was found to be more cost effective than active vapor extraction for concentrations below 500 parts per million by volume (ppm) of carbon tetrachloride. For wells that average 5-stdft{sup 3}/min air flow rates, passive vapor extraction is more cost effective below 100 ppm.

  12. The lithium vapor box divertor

    NASA Astrophysics Data System (ADS)

    Goldston, R. J.; Myers, R.; Schwartz, J.

    2016-02-01

    It has long been recognized that volumetric dissipation of the plasma heat flux from a fusion power system is preferable to its localized impingement on a material surface. Volumetric dissipation mitigates both the anticipated very high heat flux and intense particle-induced damage due to sputtering. Recent projections to a tokamak demonstration power plant suggest an immense upstream parallel heat flux, of order 20 GW m-2, implying that fully detached operation may be a requirement for the success of fusion power. Building on pioneering work on the use of lithium by Nagayama et al and by Ono et al as well as earlier work on the gas box divertor by Watkins and Rebut, we present here a concept for a lithium vapor box divertor, in which lithium vapor extracts momentum and energy from a fusion-power-plant divertor plasma, using fully volumetric processes. At the high powers and pressures that are projected this requires a high density of lithium vapor, which must be isolated from the main plasma in order to avoid lithium build-up on the chamber walls or in the plasma. Isolation is achieved through a powerful multi-box differential pumping scheme available only for condensable vapors. The preliminary box-wise calculations are encouraging, but much more work is required to demonstrate the practical viability of this scheme, taking into account at least 2D plasma and vapor flows within and between the vapor boxes and out of the vapor boxes to the main plasma.

  13. Field comparison of methods for the measurement of gaseous and particulate contributors to acidic dry deposition

    SciTech Connect

    Sickles, J.E.; Hodson, L.L.; McClenny, W.A.; Paur, R.J.; Ellestad, T.G.

    1990-01-01

    A field study was conducted to compare methods for sampling and analysis of atmospheric constituents that are important contributors to acidic dry deposition. Three multicomponent samplers were used: the Canadian filter pack (FP), the annular denuder system (ADS), and the transition flow reactor (TFR). A tunable diode laser absorption spectrometer (TDLAS) provided continuous reference measurements of NO2 and HNO3. Nitrogen dioxide was also monitored with continuous luminol-based chemiluminescence monitors and with passive sampling devices (PSDs). The study was designed to provide a database for statistical comparison of the various methods with emphasis on the multicomponent samplers under consideration for use in a national dry deposition network. The study was conducted at the EPA dry deposition station in Research Triangle Park, NC between 29 September and 12 October, 1986. Daily averaging and/or sampling times were employed for the 13-day study; weekly samples were also collected, but results from these samples are not compared in the paper. Different measurements of ambient concentrations of the following constituents are compared: total particulate and gaseous NO3(-), HNO3, NO2, total particulate NH4(-), NH3, total particulate SO4(-), and SO2.

  14. VAPOR SHIELD FOR INDUCTION FURNACE

    DOEpatents

    Reese, S.L.; Samoriga, S.A.

    1958-03-11

    This patent relates to a water-cooled vapor shield for an inductlon furnace that will condense metallic vapors arising from the crucible and thus prevent their condensation on or near the induction coils, thereby eliminating possible corrosion or shorting out of the coils. This is accomplished by placing, about the top, of the crucible a disk, apron, and cooling jacket that separates the area of the coils from the interior of the cruclbIe and provides a cooled surface upon whlch the vapors may condense.

  15. Precision ozone vapor pressure measurements

    NASA Technical Reports Server (NTRS)

    Hanson, D.; Mauersberger, K.

    1985-01-01

    The vapor pressure above liquid ozone has been measured with a high accuracy over a temperature range of 85 to 95 K. At the boiling point of liquid argon (87.3 K) an ozone vapor pressure of 0.0403 Torr was obtained with an accuracy of + or - 0.7 percent. A least square fit of the data provided the Clausius-Clapeyron equation for liquid ozone; a latent heat of 82.7 cal/g was calculated. High-precision vapor pressure data are expected to aid research in atmospheric ozone measurements and in many laboratory ozone studies such as measurements of cross sections and reaction rates.

  16. Chemical vapor deposition growth

    NASA Technical Reports Server (NTRS)

    Ruth, R. P.; Manasevit, H. M.; Campbell, A. G.; Johnson, R. E.; Kenty, J. L.; Moudy, L. A.; Shaw, G. L.; Simpson, W. I.; Yang, J. J.

    1978-01-01

    The objective was to investigate and develop chemical vapor deposition (CVD) techniques for the growth of large areas of Si sheet on inexpensive substrate materials, with resulting sheet properties suitable for fabricating solar cells that would meet the technical goals of the Low Cost Silicon Solar Array Project. The program involved six main technical tasks: (1) modification and test of an existing vertical-chamber CVD reactor system; (2) identification and/or development of suitable inexpensive substrate materials; (3) experimental investigation of CVD process parameters using various candidate substrate materials; (4) preparation of Si sheet samples for various special studies, including solar cell fabrication; (5) evaluation of the properties of the Si sheet material produced by the CVD process; and (6) fabrication and evaluation of experimental solar cell structures, using impurity diffusion and other standard and near-standard processing techniques supplemented late in the program by the in situ CVD growth of n(+)/p/p(+) sheet structures subsequently processed into experimental cells.

  17. Supercritical microgravity droplet vaporization

    NASA Technical Reports Server (NTRS)

    Hartfield, J.; Curtis, E.; Farrell, P.

    1990-01-01

    Supercritical droplet vaporization is an important issue in many combustion systems, such as liquid fueled rockets and compression-ignition (diesel) engines. In order to study the details of droplet behavior at these conditions, an experiment was designed to provide a gas phase environment which is above the critical pressure and critical temperature of a single liquid droplet. In general, the droplet begins as a cold droplet in the hot, high pressure environment. In order to eliminate disruptions to the droplet by convective motion in the gas, forced and natural convection gas motion are required to be small. Implementation of this requirement for forced convection is straightforward, while reduction of natural convection is achieved by reduction in the g-level for the experiment. The resulting experiment consists of a rig which can stably position a droplet without restraint in a high-pressure, high temperature gas field in microgravity. The microgravity field is currently achieved by dropping the device in the NASA Lewis 2.2 second drop tower. The performance of the experimental device and results to date are presented.

  18. Multiwavelength Strontium Vapor Lasers

    NASA Astrophysics Data System (ADS)

    Soldatov, A. N.; Yudin, N. A.

    2016-08-01

    Based on an analysis of experimental and theoretical works, modern notion on conditions of forming of population density inversion on self-terminating IR transitions of alkali-earth metals is given. It is demonstrated that there is a significant difference in the inversion formation in lasers on self-terminating transitions in the visible and near-IR ranges and lasers on self-terminating transitions of alkali-earth metals lasing IR lines in the mid-IR range. It is shown that in the discharge circuit of lasers on self-terminating metal atom transitions (LSMT) there are processes strengthening the influence of the known mechanism limiting the frequency and energy characteristics (FEC) of radiation caused by the presence of prepulse electron concentration. The mechanism of influence of these processes on FEC of the LSMT and technical methods of their neutralization are considered. The possibility of obtaining average lasing power of ~200 W from one liter volume of the active medium of the strontium vapor laser is demonstrated under conditions of neutralization of these processes.

  19. Dimers in nucleating vapors

    NASA Astrophysics Data System (ADS)

    Lushnikov, A. A.; Kulmala, M.

    1998-09-01

    The dimer stage of nucleation may affect considerably the rate of the nucleation process at high supersaturation of the nucleating vapor. Assuming that the dimer formation limits the nucleation rate, the kinetics of the particle formation-growth process is studied starting with the definition of dimers as bound states of two associating molecules. The partition function of dimer states is calculated by summing the Boltzmann factor over all classical bound states, and the equilibrium population of dimers is found for two types of intermolecular forces: the Lennard-Jones (LJ) and rectangular well+hard core (RW) potentials. The principle of detailed balance is used for calculating the evaporation rate of dimers. The kinetics of the particle formation-growth process is then investigated under the assumption that the trimers are stable with respect to evaporation and that the condensation rate is a power function of the particle mass. If the power exponent λ=n/(n+1) (n is a non-negative integer), the kinetics of the process is described by a finite set of moments of particle mass distribution. When the characteristic time of the particle formation by nucleation is much shorter than that of the condensational growth, n+2 universal functions of a nondimensional time define the kinetic process. These functions are calculated for λ=2/3 (gas-to-particle conversion in the free molecular regime) and λ=1/2 (formation of islands on surfaces).

  20. Medicinal Cannabis: In Vitro Validation of Vaporizers for the Smoke-Free Inhalation of Cannabis

    PubMed Central

    Lanz, Christian; Mattsson, Johan; Soydaner, Umut; Brenneisen, Rudolf

    2016-01-01

    Inhalation by vaporization is a promising application mode for cannabis in medicine. An in vitro validation of 5 commercial vaporizers was performed with THC-type and CBD-type cannabis. Gas chromatography/mass spectrometry was used to determine recoveries of total THC (THCtot) and total CBD (CBDtot) in the vapor. High-performance liquid chromatography with photodiode array detection was used for the quantitation of acidic cannabinoids in the residue and to calculate decarboxylation efficiencies. Recoveries of THCtot and CBDtot in the vapor of 4 electrically-driven vaporizers were 58.4 and 51.4%, 66.8 and 56.1%, 82.7 and 70.0% and 54.6 and 56.7% for Volcano Medic®, Plenty Vaporizer®, Arizer Solo® and DaVinci Vaporizer®, respectively. Decarboxylation efficiency was excellent for THC (≥ 97.3%) and CBD (≥ 94.6%). The gas-powered Vape-or-Smoke™ showed recoveries of THCtot and CBDtot in the vapor of 55.9 and 45.9%, respectively, and a decarboxylation efficiency of ≥ 87.7 for both cannabinoids. However, combustion of cannabis was observed with this device. Temperature-controlled, electrically-driven vaporizers efficiently decarboxylate inactive acidic cannabinoids and reliably release their corresponding neutral, active cannabinoids. Thus, they offer a promising application mode for the safe and efficient administration of medicinal cannabis. PMID:26784441

  1. Liquid-phase and vapor-phase dehydration of organic/water solutions

    DOEpatents

    Huang, Yu; Ly, Jennifer; Aldajani, Tiem; Baker, Richard W.

    2011-08-23

    Processes for dehydrating an organic/water solution by pervaporation or vapor separation using fluorinated membranes. The processes are particularly useful for treating mixtures containing light organic components, such as ethanol, isopropanol or acetic acid.

  2. CORRECTION FACTORS FOR COVARIANCE BETWEEN CONCENTRATION AND DEPOSITION VELOCITY ON CASTNET HNO3 DEPOSITION ESTIMATES

    EPA Science Inventory

    The covariance between hourly concentration (C) and deposition velocity (V) for various atmospheric; species may act to bias the, deposition (D) computed from the product of the weekly average C and 'V. This is a potential problem for the CASTNet filter pack (FP) species, nitric...

  3. Soil Vapor Extraction Implementation Experiences

    EPA Pesticide Factsheets

    This issue paper identifies issues and summarizes experiences with soil vapor extraction (SVE) as a remedy for volatile organic compounds (VOCs) in soils. The issues presented here reflect discussions with over 30 Remedial Project Managers (RPMs)...

  4. Understanding Latent Heat of Vaporization.

    ERIC Educational Resources Information Center

    Linz, Ed

    1995-01-01

    Presents a simple exercise for students to do in the kitchen at home to determine the latent heat of vaporization of water using typical household materials. Designed to stress understanding by sacrificing precision for simplicity. (JRH)

  5. Tubing For Sampling Hydrazine Vapor

    NASA Technical Reports Server (NTRS)

    Travis, Josh; Taffe, Patricia S.; Rose-Pehrsson, Susan L.; Wyatt, Jeffrey R.

    1993-01-01

    Report evaluates flexible tubing used for transporting such hypergolic vapors as those of hydrazines for quantitative analysis. Describes experiments in which variety of tubing materials, chosen for their known compatibility with hydrazine, flexibility, and resistance to heat.

  6. Portable vapor diffusion coefficient meter

    DOEpatents

    Ho, Clifford K.

    2007-06-12

    An apparatus for measuring the effective vapor diffusion coefficient of a test vapor diffusing through a sample of porous media contained within a test chamber. A chemical sensor measures the time-varying concentration of vapor that has diffused a known distance through the porous media. A data processor contained within the apparatus compares the measured sensor data with analytical predictions of the response curve based on the transient diffusion equation using Fick's Law, iterating on the choice of an effective vapor diffusion coefficient until the difference between the predicted and measured curves is minimized. Optionally, a purge fluid can forced through the porous media, permitting the apparatus to also measure a gas-phase permeability. The apparatus can be made lightweight, self-powered, and portable for use in the field.

  7. Vapor deposition of hardened niobium

    DOEpatents

    Blocher, Jr., John M.; Veigel, Neil D.; Landrigan, Richard B.

    1983-04-19

    A method of coating ceramic nuclear fuel particles containing a major amount of an actinide ceramic in which the particles are placed in a fluidized bed maintained at ca. 800.degree. to ca. 900.degree. C., and niobium pentachloride vapor and carbon tetrachloride vapor are led into the bed, whereby niobium metal is deposited on the particles and carbon is deposited interstitially within the niobium. Coating apparatus used in the method is also disclosed.

  8. Collapse of large vapor bubbles

    NASA Technical Reports Server (NTRS)

    Tegart, J.; Dominick, S.

    1982-01-01

    The refilling of propellant tanks while in a low-gravity environment requires that entrapped vapor bubbles be collapsed by increasing the system pressure. Tests were performed to verify the mechanism of collapse for these large vapor bubbles with the thermodynamic conditions, geometry, and boundary conditions being those applicable to propellant storage systems. For these conditions it was found that conduction heat transfer determined the collapse rate, with the specific bubble geometry having a significant influence.

  9. Dilute nitric or nitrous acid solution containing halide ions as effective media for pure gold dissolution.

    PubMed

    Hojo, Masashi; Yamamoto, Masahiko; Okamura, Kei

    2015-08-14

    The greatly enhanced oxidation ability of dilute aqueous nitric acid (0.10-2.0 mol L(-1)) containing bromide and iodide salts as well as chloride salts has been examined based on the dissolution kinetics of pure gold at 30-60 °C. It has been found that bromide salts are more effective than chloride salts in gaining the ability of dissolving gold in dilute aqueous nitric acid solution. At 60 °C, a piece of gold-wire (ca. 20 mg) is dissolved in 20 mL of as low as 0.10 mol L(-1) HNO3 solution containing 1.0-5.0 mol L(-1) NaBr and the dissolution rate constant, log(k/s(-1)), increases linearly (from -5.78 to -4.52) with the increasing NaBr concentration. The addition of organic solvents, such as acetonitrile and acetic acid, causes acceleration of gold dissolution in LiBr and NaBr solutions. With increasing MeCN contents, for instance, the log(k/s(-1)) value of 0.10 mol L(-1) HNO3 solution containing 2.0 mol L(-1) NaBr increases linearly from -5.30 to -4.61 at 30% (v/v) MeCN. The bromide salts affect the gold dissolution rate constant in the order of KBr < NaBr < LiBr < CaBr2. With increasing NaI concentration (0.20-3.0 mol L(-1)), some acceleration in log(k/s(-1)) of 0.50 or 1.0 mol L(-1) HNO3 solution has been observed; however, the slope of acceleration as the function of NaI concentration is much smaller than that of NaCl or NaBr. The gold dissolution ability has been examined also for nitrous acid containing chloride and bromide ions at 35 °C. The NaNO2 solution containing twice or more amounts of HX (X = Cl, Br) gives the maximum efficiency for gold dissolution, according to the log(k/s(-1)) values of the mixed solutions of NaNO2 (0.10-2.0 mol L(-1)) and HX of various concentrations. The influence of oxidation by dilute nitric and nitrous acids on the gold dissolution is discussed from the standpoint of the redox potentials in "modified" aqueous solutions and not of the changes in the activity coefficients of ions.

  10. Measurements of ozone, nitrogen dioxide, nitrous and nitric acids, and sulphur dioxide in the Eastern Mediterranean

    NASA Astrophysics Data System (ADS)

    Vecera, V.; Mikuska, M.; Smolik, S.; Eleftheriadis, E.; Bryant, B.; Colbeck, C.; Lazaridis, L.

    2003-04-01

    Measurements of reactive nitrogen gases (NO_2, HONO, HNO_3), as well as ozone and sulfur dioxide were made over the Aegean Sea (the R/V Agaeon) within an air mass later reaching the Finokalia (Crete) sampling site. These measurements were carried out with unique gas trace instrumentation (wet effluent and "dry" diffusion denuder techniques, a chemiluminescent detection and chemiluminescent analyzers) during special conditions. There are significant differences in pollutant concentrations between results from Finokalia and from the R/V Agaeon. While at Finokalia concentrations of nitrogen dioxide, ozone and nitric and nitrous acids changed relatively slowly, the boat data showed a number of episodes with rapid changes in reactive nitrogen compounds and ozone concentrations. These episodes were correlated with the presence of boats up wind a short distance from the R/V Agaeon. Ozone concentrations at Finokalia and on the boat typically ranged between 40--80 ppb (v/v). Ozone concentrations reached up to 88 ppb (v/v) in the open sea. Nitrogen dioxide concentrations at Finokalia were in the range 0.5--3 ppb (v/v). Typical NO_2 concentrations observed aboard the boat were 4--6 ppb (v/v) with maxima of 20--30 ppb (v/v). During "spiked" episodes, up to 200 ppb (v/v) of nitrogen dioxide was observed while ozone concurrently was dramatically depleted down to 20 ppb (v/v). Concentrations of HONO and HNO_3 at Finokalia, in general, were low, typically in the order of 0.1--0.2 ppb (v/v) for HONO and 0.05--0.1 ppb (v/v) for HNO_3. On average, concentrations of both nitric and nitrous acids in the ambient air of the Aegean Sea were typically small, below 0.05 ppt (v/v). Within the "spiked" episodes up to 33 ppb (v/v) nitric acid and up to 2.5 ppb (v/v) nitrous acid were formed. The nitric acid "dry" denuder data were on average higher than the measurements by the wet efluent diffusion denuder. The concentration of SO_2 reached up to 9.2 ppb (v/v). The work was conducted within

  11. Finding organic vapors - a Monte Carlo approach

    NASA Astrophysics Data System (ADS)

    Vuollekoski, Henri; Boy, Michael; Kerminen, Veli-Matti; Kulmala, Markku

    2010-05-01

    Aerosols have an important role in regulating the climate both directly by absorbing and scattering solar radiation, as well as indirectly by acting as cloud condensation nuclei. While it is known that their net effect on radiative forcing is negative, several key aspects remain mysterious. There exist plenty of known primary sources of particles due to both natural and man-made origin - for example desert dust, volcanic activity and tire debris. On the other hand, it has been shown that the formation of secondary particles, by nucleation from precursor vapors, is a frequent, global phenomenon. However, the very earliest steps in new particle formation - nucleation and early growth by condensation - have many big question marks on them. While several studies have indicated the importance of a sufficient concentration of sulphuric acid vapor for the process, it has also been noted that this is usually not enough. Heads have therefore turned to organic vapors, which in their multitude could explain various observed characteristics of new particle formation. But alas, the vast number of organic compounds, their complex chemistry and properties that make them difficult to measure, have complicated the quantifying task. Nevertheless, evidence of organic contribution in particles of all size classes has been found. In particular, a significant organic constituent in the very finest particles suggests the presence of a high concentration of very low-volatile organic vapors. In this study, new particle formation in the boreal forest environment of Hyytiälä, Finland, is investigated in a process model. Our goal is to quantify the concentration, to find the diurnal profile and to get hints of the identity of some organic vapors taking part in new particle formation. Previous studies on the subject have relied on data analysis of the growth rate of the observed particles. However, due to the coarse nature of the methods used to calculate growth rates, this approach has its

  12. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  13. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  14. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  15. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  16. 21 CFR 868.5880 - Anesthetic vaporizer.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Anesthetic vaporizer. 868.5880 Section 868.5880...) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5880 Anesthetic vaporizer. (a) Identification. An anesthetic vaporizer is a device used to vaporize liquid anesthetic and deliver a...

  17. Heterogeneous reactions of gaseous hydrogen peroxide on pristine and acidic gas-processed calcium carbonate particles: Effects of relative humidity and surface coverage of coating

    NASA Astrophysics Data System (ADS)

    Zhao, Yue; Chen, Zhongming; Shen, Xiaoli; Huang, Dao

    2013-03-01

    Atmospheric aging appears to alter physical and chemical properties of mineral dust aerosol and thus its role as reactive surface in the troposphere. Yet, previous studies in the atmosphere have mainly focused on the pristine surfaces of mineral dust aerosol, and the reactivity of aged mineral dust toward atmospheric trace gases is poorly recognized. This work presents the first laboratory investigation of heterogeneous reactions of gaseous hydrogen peroxide (H2O2), an important atmospheric oxidant, on the surfaces of HNO3 and SO2-processed calcium carbonate particles as surrogates of atmospheric mineral dust aged by acidic trace gases. It is found that the processing of the calcium carbonate particles with HNO3 and SO2 has a strong impact on their reactivity toward H2O2. On HNO3-processed particles, the presence of nitrate acts to either decrease or increase H2O2 uptake, greatly depending on RH and surface coverage of nitrate. On SO2-processed particles, the presence of surface sulfite appears to enhance the intrinsic reactivity of the mineral particles due to its affinity for H2O2, and the uptake of H2O2 increases significantly relative to the pristine particles, in particular at high RH. The mechanisms for heterogeneous reactions of H2O2 with these processed particles are discussed, as well as their potential implications on tropospheric chemistry. The results of our study suggest that the reactivity of mineral dust aerosol toward H2O2 and maybe other trace gases is markedly dependent on the chemical composition and coverage of the coatings as well as ambient RH, and thus will vary considerably in different polluted air masses.

  18. Recent advances in vapor intrusion site investigations.

    PubMed

    McHugh, Thomas; Loll, Per; Eklund, Bart

    2017-02-22

    Our understanding of vapor intrusion has evolved rapidly since the discovery of the first high profile vapor intrusion sites in the late 1990s and early 2000s. Research efforts and field investigations have improved our understanding of vapor intrusion processes including the role of preferential pathways and natural barriers to vapor intrusion. This review paper addresses recent developments in the regulatory framework and conceptual model for vapor intrusion. In addition, a number of innovative investigation methods are discussed.

  19. The atmospheric water vapor line.

    NASA Astrophysics Data System (ADS)

    Strong, M.; Sharp, Z. D.; Gutzler, D. S.

    2008-12-01

    We have measured the hydrogen and oxygen isotope composition of atmospheric water vapor periodically across the American Southwest through most of 2007. Samples were primarily collected over Albuquerque, NM on the roof of the 3-story UNM geology building on a near-daily basis with occasional sampling in southern Arizona and southern Texas. Water vapor was captured by pumping ~60 to ~600 liters of air (amount depending on dew point) through a cold trap, producing ~1mL of water. Precipitation samples were also collected in Albuquerque throughout the year and analyzed for hydrogen and oxygen isotopic composition. Isotopic compositions of both vapor and precipitation were determined by CO2 equilibration for oxygen and chromium reduction for hydrogen, with resulting gasses analyzed on a mass spectrometer. Nearly all water vapor samples lie parallel to the Global Meteoric Water Line (GMWL) but with a deuterium excess of ~17 (δD = 8δO + 17). This is true regardless of relative humidity, dew point, location, time of day, or season. Precipitation samples fall to the right of the GMWL with a slope of ~5. Within our dataset we have identified 10 pairs of vapor and precipitation samples that were collected within 24 hours. Half of these sample pairs have values consistent with equilibrium conditions at ground temperature, while the other half are not in equilibrium at any temperature. Simple modeling of nonequilibrium fractionation processes suggests that the array of precipitation samples can be derived from the array of vapor samples by equilibrium condensation followed by partial evaporation of falling raindrops. Our data suggests that atmospheric water vapor has a relatively constant deuterium excess value regardless of moisture source, degree of rainout, and/or evapotranspiration contributions.

  20. The lithium vapor box divertor

    DOE PAGES

    Goldston, R. J.; Myers, R.; Schwartz, J.

    2016-01-13

    It has long been recognized that volumetric dissipation of the plasma heat flux from a fusion power system is preferable to its localized impingement on a material surface. Volumetric dissipation mitigates both the anticipated very high heat flux and intense particle-induced damage due to sputtering. Our recent projections to a tokamak demonstration power plant suggest an immense upstream parallel heat flux, of order 20 GW m-2, implying that fully detached operation may be a requirement for the success of fusion power. Building on pioneering work on the use of lithium by Nagayama et al and by Ono et al asmore » well as earlier work on the gas box divertor by Watkins and Rebut, we present here a concept for a lithium vapor box divertor, in which lithium vapor extracts momentum and energy from a fusion-power-plant divertor plasma, using fully volumetric processes. Furthermore, at the high powers and pressures that are projected this requires a high density of lithium vapor, which must be isolated from the main plasma in order to avoid lithium build-up on the chamber walls or in the plasma. Isolation is achieved through a powerful multi-box differential pumping scheme available only for condensable vapors. The preliminary box-wise calculations are encouraging, but much more work is required in order to demonstrate the practical viability of this scheme, taking into account at least 2D plasma and vapor flows within and between the vapor boxes and out of the vapor boxes to the main plasma.« less

  1. The lithium vapor box divertor

    SciTech Connect

    Goldston, R. J.; Myers, R.; Schwartz, J.

    2016-01-13

    It has long been recognized that volumetric dissipation of the plasma heat flux from a fusion power system is preferable to its localized impingement on a material surface. Volumetric dissipation mitigates both the anticipated very high heat flux and intense particle-induced damage due to sputtering. Our recent projections to a tokamak demonstration power plant suggest an immense upstream parallel heat flux, of order 20 GW m-2, implying that fully detached operation may be a requirement for the success of fusion power. Building on pioneering work on the use of lithium by Nagayama et al and by Ono et al as well as earlier work on the gas box divertor by Watkins and Rebut, we present here a concept for a lithium vapor box divertor, in which lithium vapor extracts momentum and energy from a fusion-power-plant divertor plasma, using fully volumetric processes. Furthermore, at the high powers and pressures that are projected this requires a high density of lithium vapor, which must be isolated from the main plasma in order to avoid lithium build-up on the chamber walls or in the plasma. Isolation is achieved through a powerful multi-box differential pumping scheme available only for condensable vapors. The preliminary box-wise calculations are encouraging, but much more work is required in order to demonstrate the practical viability of this scheme, taking into account at least 2D plasma and vapor flows within and between the vapor boxes and out of the vapor boxes to the main plasma.

  2. A Thermochemical Kinetic-Based Study of Ignition Delays for 2-Azidoethanamine-Red Fuming Nitric Acid Systems: 2-Azido-N-Methylethanamine (MMAZ) Vs. 2-Azido-N,N-Dimethylethanamine (DMAZ)

    DTIC Science & Technology

    2014-01-01

    and DMAZ-RFNA systems. Table 2. Complexation exothermicities (in kcal/mol): MMAZ-(HNO3)x vs . DMAZ-(HNO3)x. a Reaction CBS-QB3 G4 G3MP2B3 G3MP2...5 Table 2. Complexation exothermicities (in kcal/mol): MMAZ-(HNO3)x vs . DMAZ-(HNO3)x...structures for MMAZ-(HNO3)x complexes. (Bond distances in Å.) Table 2 lists the exothermicities that were computed for the reactions leading to these

  3. Condensed Acids In Antartic Stratospheric Clouds

    NASA Technical Reports Server (NTRS)

    Pueschel, R. F.; Snetsinger, K. G.; Toon, O. B.; Ferry, G. V.; Starr, W. L.; Oberbeck, V. R.; Chan, K. R.; Goodman, J. K.; Livingston, J. M.; Verma, S.; Fong, W.

    1992-01-01

    Report dicusses nitrate, sulfate, and chloride contents of stratospheric aerosols during 1987 Airborne Antarctic Ozone Experiment. Emphasizes growth of HNO3*3H2O particles in polar stratospheric clouds. Important in testing theories concerning Antarctic "ozone hole".

  4. Extraction of transplutionium and rare-earth elements, molybdenum and iron with zirconium salt of dibutyl phosphoric acid

    NASA Astrophysics Data System (ADS)

    Zilberman, B. Ya.; Fedorov, Yu. S.; Shmidt, O. V.; Goletsky, N. D.; Sukhareva, S. Yu.; Puzikov, E. A.; Suglobov, D. N.; Mashirov, L. G.; Choppin, G. R.

    2003-01-01

    Zirconium salt of dibutyl phosphoric acid (ZS-HDBP) dissolved in dilute tributyl phosphate (TBP) is proposed as a solvent for separation of transplutonium and rare-earth elements (TPE, RE), including yttrium, from high-level waste in the presence of molybdenum and iron. The optimum HDBP:Zr ratio is 9 for RE and TPE extraction and is 12.5 for Mo. IR spectra indicate formation of Zr(DBP)4(HDBP)4 complex as a base of solvation. HNO3 depresses RE and TPE extraction, while Mo extraction is characterised by a minimum at 2.5 mol/L HNO3. Presence of TBP in the solvent, independently of the used diluent, leads to reduction of the distribution coefficients, but ZS-HDBP extraction capacity for the above elements is increased, as well as solubility of their solvates. Two types of complexes M(DBP)3 and MNO3(DBP)2 are formed at RE and TPE extraction by ZS-HDBP in dilute TBP. Molybdenum extraction is based both on cation exchange and on Mo solvation with HDBP as a neutral ligand. Iron extraction is formally similar to that of Mo, being influenced by the latter if both metals are present in the solution.

  5. Corrosion investigations on zircaloy-4 and titanium dissolver materials for MOX fuel dissolution in concentrated nitric acid containing fluoride ions

    NASA Astrophysics Data System (ADS)

    Jayaraj, J.; Krishnaveni, P.; Krishna, D. Nanda Gopala; Mallika, C.; Mudali, U. Kamachi

    2016-05-01

    Aqueous reprocessing of plutonium-rich mixed oxide fuels require fluoride as a dissolution catalyst in boiling nitric acid for an effective dissolution of the spent fuel. High corrosion rates were obtained for the candidate dissolver materials zircaloy-4 (Zr-4) and commercial pure titanium (CP-Ti grade 2) in boiling 11.5 M HNO3 + 0.05 M NaF. Complexing the fluoride ions either with Al(NO3)3 or ZrO(NO3)2 aided in decreasing the corrosion rates of Zr-4 and CP-Ti. From the obtained corrosion rates it is concluded that CP-Ti is a better dissolver material than Zr-4 for extended service life in boiling 11.5 M HNO3 + 0.05 M NaF, when complexed with 0.15 M ZrO(NO3)2. XPS analysis confirmed the presence of TiO2 and absence of fluoride on the surface of CP-Ti samples, indicating that effective complexation had occurred in solution leading to passivation of the metal and imparting high corrosion resistance.

  6. A new facile route for synthesizing of graphene oxide using mixture of sulfuric-nitric-phosphoric acids as intercalating agent

    NASA Astrophysics Data System (ADS)

    Panwar, Vinay; Chattree, Ananya; Pal, Kaushik

    2015-09-01

    In this work, graphene oxide (GO) has been prepared through three different processes namely, eco-friendly Hummers method, modification in improved Hummers method and a new approach. This new approach has been designed by changing some processing parameters and intercalating agent for significant reduction in processing time and to improve the quantity of GO in comparison to the other two methods. This has been achieved through better oxidization of graphite using nitric-sulfuric acid (HNO3-H2SO4) as intercalating agent. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, Atomic Force Microscopy (AFM), X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, and Thermogravimetric analysis (TGA) are used to characterize the GO prepared through different processes. These characterizations have confirmed an improved exfoliation of graphite, using addition of HNO3 in intercalating agent, in a short processing time and bring on higher yield of GO via this new process.

  7. 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.

  8. Potentiometric detection of chemical vapors using molecularly imprinted polymers as receptors

    NASA Astrophysics Data System (ADS)

    Liang, Rongning; Chen, Lusi; Qin, Wei

    2015-07-01

    Ion-selective electrode (ISE) based potentiometric gas sensors have shown to be promising analytical tools for detection of chemical vapors. However, such sensors are only capable of detecting those vapors which can be converted into ionic species in solution. This paper describes for the first time a polymer membrane ISE based potentiometric sensing system for sensitive and selective determination of neutral vapors in the gas phase. A molecularly imprinted polymer (MIP) is incorporated into the ISE membrane and used as the receptor for selective adsorption of the analyte vapor from the gas phase into the sensing membrane phase. An indicator ion with a structure similar to that of the vapor molecule is employed to indicate the change in the MIP binding sites in the membrane induced by the molecular recognition of the vapor. The toluene vapor is used as a model and benzoic acid is chosen as its indicator. Coupled to an apparatus manifold for preparation of vapor samples, the proposed ISE can be utilized to determine volatile toluene in the gas phase and allows potentiometric detection down to parts per million levels. This work demonstrates the possibility of developing a general sensing principle for detection of neutral vapors using ISEs.

  9. Potentiometric detection of chemical vapors using molecularly imprinted polymers as receptors

    PubMed Central

    Liang, Rongning; Chen, Lusi; Qin, Wei

    2015-01-01

    Ion-selective electrode (ISE) based potentiometric gas sensors have shown to be promising analytical tools for detection of chemical vapors. However, such sensors are only capable of detecting those vapors which can be converted into ionic species in solution. This paper describes for the first time a polymer membrane ISE based potentiometric sensing system for sensitive and selective determination of neutral vapors in the gas phase. A molecularly imprinted polymer (MIP) is incorporated into the ISE membrane and used as the receptor for selective adsorption of the analyte vapor from the gas phase into the sensing membrane phase. An indicator ion with a structure similar to that of the vapor molecule is employed to indicate the change in the MIP binding sites in the membrane induced by the molecular recognition of the vapor. The toluene vapor is used as a model and benzoic acid is chosen as its indicator. Coupled to an apparatus manifold for preparation of vapor samples, the proposed ISE can be utilized to determine volatile toluene in the gas phase and allows potentiometric detection down to parts per million levels. This work demonstrates the possibility of developing a general sensing principle for detection of neutral vapors using ISEs. PMID:26215887

  10. Electrical Breakdown in Water Vapor

    SciTech Connect

    Skoro, N.; Maric, D.; Malovic, G.; Petrovic, Z. Lj.; Graham, W. G.

    2011-11-15

    In this paper investigations of the voltage required to break down water vapor are reported for the region around the Paschen minimum and to the left of it. In spite of numerous applications of discharges in biomedicine, and recent studies of discharges in water and vapor bubbles and discharges with liquid water electrodes, studies of the basic parameters of breakdown are lacking. Paschen curves have been measured by recording voltages and currents in the low-current Townsend regime and extrapolating them to zero current. The minimum electrical breakdown voltage for water vapor was found to be 480 V at a pressure times electrode distance (pd) value of around 0.6 Torr cm ({approx}0.8 Pa m). The present measurements are also interpreted using (and add additional insight into) the developing understanding of relevant atomic and particularly surface processes associated with electrical breakdown.

  11. Vapor deposition of thin films

    DOEpatents

    Smith, David C.; Pattillo, Stevan G.; Laia, Jr., Joseph R.; Sattelberger, Alfred P.

    1992-01-01

    A highly pure thin metal film having a nanocrystalline structure and a process of preparing such highly pure thin metal films of, e.g., rhodium, iridium, molybdenum, tungsten, rhenium, platinum, or palladium by plasma assisted chemical vapor deposition of, e.g., rhodium(allyl).sub.3, iridium(allyl).sub.3, molybdenum(allyl).sub.4, tungsten(allyl).sub.4, rhenium(allyl).sub.4, platinum(allyl).sub.2, or palladium(allyl).sub.2 are disclosed. Additionally, a general process of reducing the carbon content of a metallic film prepared from one or more organometallic precursor compounds by plasma assisted chemical vapor deposition is disclosed.

  12. Reevaluation of Neptunium-Nitric Acid Radiation Chemistry by Multiscale Modeling.

    PubMed

    Horne, G P; Grimes, T S; Mincher, B J; Mezyk, S P

    2016-12-15

    Multiscale modeling has been used to quantitatively reevaluate the radiation chemistry of neptunium in a range of aerated nitric acid solutions (0.1-6.0 mol dm(-3)). Exact calculation of initial radiolytic yields accounting for changes in radiation track chemistry was found to be crucial for reproducing experimental data. The γ irradiation induces changes in the Np(VI)/Np(V) oxidation-state distribution, predominantly driven by reactions involving HNO2, H2O2, NO2(•), and NO3(•) from the radiolysis of aqueous nitric acid. Oxidation of Np(V) by NO3(•) (k = 8.1 × 10(8) dm(3) mol(-1) s(-1)) provides the initial increase in Np(VI) concentration, while also delaying net reduction of Np(VI) by consuming HNO2. Reduction of Np(VI) is dominated by thermal reactions with HNO2 (k = 0.7-73 dm(3) mol(-1) s(-1)) and H2O2 (k = 1.9 dm(3) mol(-1) s(-1)). A steady state is eventually established once the concentration of Np(V) is sufficiently high to be oxidized by NO2(•) (k = 2.4 × 10(2)-3.1 × 10(4) dm(3) mol(-1) s(-1)). An additional thermal oxidation reaction between Np(V) and HNO3 (k = 2.0 × 10(3) dm(3) mol(-1) s(-1)) is required for nitric acid concentrations >4.0 mol dm(-3). For 0.1 mol dm(-3) HNO3, the rate of Np(VI) reduction is in excess of that which can be accounted for by radiolytic product mass balance, suggesting the existence of a catalytic-acid-dependent reduction process.

  13. THERMODYNAMIC AND TRANSPORT PROPERTIES OF RUBIDIUM VAPOR AND CESIUM VAPOR

    DTIC Science & Technology

    consideration. It is assumed that the vapors are comprised of alkali atoms whose interactions are the pairwise Lennard - Jones (6 - 12) type. On the basis of...the 2 parameters which occur in the Lennard - Jones potential for interactions between some alkalis and noble gas atoms and the known parameters for the

  14. Summer-time distribution of air pollutants in Sequoia National Park, California.

    PubMed

    Bytnerowicz, Andrzej; Tausz, Michael; Alonso, Rocio; Jones, David; Johnson, Ronald; Grulke, Nancy

    2002-01-01

    Concentrations of air pollutants were monitored during the May November 1999 period on a network of forested sites in Sequoia National Park, California. Measurements were conducted with: (1) active monitors for nitric oxide (NO), nitrogen dioxide (NO2) and ozone (O3); (2) honeycomb denuder/filter pack systems for nitric acid vapor (HNO3), nitrous acid vapor (HNO2), ammonia (NH3), sulfur dioxide (SO2), particulate nitrate (NO3-), ammonium (NH4+), and sulfate (SO4(2-)); and (3) passive samplers for O3, HNO3 and NO2. Elevated concentrations of O3 (seasonal means 41-71 ppb), HNO3 (seasonal means 0.4-2.9 microg/m3), NH3 (seasonal means 1.6-4.5 microg/m3), NO3 (1.1-2.0 microg/m3) and NH4+ (1.0-1.9 microg/m3) were determined. Concentrations of other pollutants were low. With increasing elevation and distance from the pollution source area of O3, NH3 and HNO3 concentrations decreased. Ammonia and NH4+ were dominant N pollutants indicating strong influence of agricultural emissions on forests and other ecosystems of the Sequoia National Park.

  15. Low level vapor verification of monomethyl hydrazine

    NASA Technical Reports Server (NTRS)

    Mehta, Narinder

    1990-01-01

    The vapor scrubbing system and the coulometric test procedure for the low level vapor verification of monomethyl hydrazine (MMH) are evaluated. Experimental data on precision, efficiency of the scrubbing liquid, instrument response, detection and reliable quantitation limits, stability of the vapor scrubbed solution, and interference were obtained to assess the applicability of the method for the low ppb level detection of the analyte vapor in air. The results indicated that the analyte vapor scrubbing system and the coulometric test procedure can be utilized for the quantitative detection of low ppb level vapor of MMH in air.

  16. Estimated vapor pressure for WTP process streams

    SciTech Connect

    Pike, J.; Poirier, M.

    2015-01-01

    Design assumptions during the vacuum refill phase of the Pulsed Jet Mixers (PJMs) in the Hanford Waste Treatment and Immobilization Plant (WTP) equate the vapor pressure of all process streams to that of water when calculating the temperature at which the vacuum refill is reduced or eliminated. WTP design authority asked the authors to assess this assumption by performing calculations on proposed feed slurries to calculate the vapor pressure as a function of temperature. The vapor pressure was estimated for each WTP waste group. The vapor pressure suppression caused by dissolved solids is much greater than the increase caused by organic components such that the vapor pressure for all of the waste group compositions is less than that of pure water. The vapor pressure for each group at 145°F ranges from 81% to 98% of the vapor pressure of water. If desired, the PJM could be operated at higher temperatures for waste groups with high dissolved solids that suppress vapor pressure. The SO4 group with the highest vapor pressure suppression could be operated up to 153°F before reaching the same vapor pressure of water at 145°F. However, most groups would reach equivalent vapor pressure at 147 to 148°F. If any of these waste streams are diluted, the vapor pressure can exceed the vapor pressure of water at mass dilution ratios greater than 10, but the overall effect is less than 0.5%.

  17. Vapor generation methods for explosives detection research

    SciTech Connect

    Grate, Jay W.; Ewing, Robert G.; Atkinson, David A.

    2012-12-01

    The generation of calibrated vapor samples of explosives compounds remains a challenge due to the low vapor pressures of the explosives, adsorption of explosives on container and tubing walls, and the requirement to manage (typically) multiple temperature zones as the vapor is generated, diluted, and delivered. Methods that have been described to generate vapors can be classified as continuous or pulsed flow vapor generators. Vapor sources for continuous flow generators are typically explosives compounds supported on a solid support, or compounds contained in a permeation or diffusion device. Sources are held at elevated isothermal temperatures. Similar sources can be used for pulsed vapor generators; however, pulsed systems may also use injection of solutions onto heated surfaces with generation of both solvent and explosives vapors, transient peaks from a gas chromatograph, or vapors generated by s programmed thermal desorption. This article reviews vapor generator approaches with emphasis on the method of generating the vapors and on practical aspects of vapor dilution and handling. In addition, a gas chromatographic system with two ovens that is configurable with up to four heating ropes is proposed that could serve as a single integrated platform for explosives vapor generation and device testing. Issues related to standards, calibration, and safety are also discussed.

  18. Method and apparatus for vapor detection

    NASA Technical Reports Server (NTRS)

    Lerner, Melvin (Inventor); Hood, Lyal V. (Inventor); Rommel, Marjorie A. (Inventor); Pettitt, Bruce C. (Inventor); Erikson, Charles M. (Inventor)

    1980-01-01

    The method disclosed herein may be practiced by passing the vapors to be sampled along a path with halogen vapor, preferably chlorine vapor, heating the mixed vapors to halogenate those of the sampled vapors subject to halogenation, removing unreacted halogen vapor, and then sensing the vapors for organic halogenated compounds. The apparatus disclosed herein comprises means for flowing the vapors, both sample and halogen vapors, into a common path, means for heating the mixed vapors to effect the halogenation reaction, means for removing unreacted halogen vapor, and a sensing device for sensing halogenated compounds. By such a method and means, the vapors of low molecular weight hydrocarbons, ketones and alcohols, when present, such as methane, ethane, acetone, ethanol, and the like are converted, at least in part, to halogenated compounds, then the excess halogen removed or trapped, and the resultant vapors of the halogenated compounds sensed or detected. The system is highly sensitive. For example, acetone in a concentration of 30 parts per billion (volume) is readily detected.

  19. Simultaneous airborne nitric acid and formic acid measurements using a chemical ionization mass spectrometer around the UK: Analysis of primary and secondary production pathways

    NASA Astrophysics Data System (ADS)

    Le Breton, Michael; Bacak, Asan; Muller, Jennifer B. A.; Xiao, Ping; Shallcross, Beth M. A.; Batt, Rory; Cooke, Michael C.; Shallcross, Dudley E.; Bauguitte, S. J.-B.; Percival, Carl J.

    2014-02-01

    The first simultaneous measurements of formic and nitric acid mixing ratios around the United Kingdom were measured on the FAAM BAe-146 research aircraft with a chemical ionization mass spectrometer using I- reagent ions at 0.8 Hz. Analysis of the whole dataset shows that formic acid and nitric acid are positively correlated as illustrated by other studies (e.g. Veres et al., 2011). However, initial evidence indicates a prominent direct source of formic acid and also a significant source when O3 levels are high, suggesting the importance of the ozonolysis of 1-alkenes. A trajectory model was able to reproduce the formic acid concentrations by both the inclusion of a primary vehicle source and production via ozonolysis of propene equivalent 1-alkene levels. Inspection of data archives implies these levels of 1-alkene are possible after 11 am, but formic acid and nitric acid plumes early in the flight are too high for the model to replicate. These data show the relationship between nitric acid and formic acid cannot solely be attributed to related photochemical production. The simultaneous measurement of HCOOH and HNO3 has been implemented to estimate OH levels along the flight track assuming a relationship between formic and nitric acid in photochemical plumes and a constant source of 1-alkene.

  20. Vacuum vapor deposition gun assembly

    DOEpatents

    Zeren, Joseph D.

    1985-01-01

    A vapor deposition gun assembly includes a hollow body having a cylindrical outer surface and an end plate for holding an adjustable heat sink, a hot hollow cathode gun, two magnets for steering the plasma from the gun into a crucible on the heat sink, and a shutter for selectively covering and uncovering the crucible.

  1. Final OSWER Vapor Intrusion Guidance

    EPA Science Inventory

    EPA is preparing to finalize its guidance on assessing and addressing vapor intrusion, which is defined as migration of volatile constituents from contaminated media in the subsurface (soil or groundwater) into the indoor environment. In November 2002, EPA issued draft guidance o...

  2. Hydrazine vapor inactivates Bacillus spores

    NASA Astrophysics Data System (ADS)

    Schubert, Wayne W.; Engler, Diane L.; Beaudet, Robert A.

    2016-05-01

    NASA policy restricts the total number of bacterial spores that can remain on a spacecraft traveling to any planetary body which might harbor life or have evidence of past life. Hydrazine, N2H4, is commonly used as a propellant on spacecraft. Hydrazine as a liquid is known to inactivate bacterial spores. We have now verified that hydrazine vapor also inactivates bacterial spores. After Bacillus atrophaeus ATCC 9372 spores deposited on stainless steel coupons were exposed to saturated hydrazine vapor in closed containers, the spores were recovered from the coupons, serially diluted, pour plated and the surviving bacterial colonies were counted. The exposure times required to reduce the spore population by a factor of ten, known as the D-value, were 4.70 ± 0.50 h at 25 °C and 2.85 ± 0.13 h at 35 °C. These inactivation rates are short enough to ensure that the bioburden of the surfaces and volumes would be negligible after prolonged exposure to hydrazine vapor. Thus, all the propellant tubing and internal tank surfaces exposed to hydrazine vapor do not contribute to the total spore count.

  3. Simple Chemical Vapor Deposition Experiment

    ERIC Educational Resources Information Center

    Pedersen, Henrik

    2014-01-01

    Chemical vapor deposition (CVD) is a process commonly used for the synthesis of thin films for several important technological applications, for example, microelectronics, hard coatings, and smart windows. Unfortunately, the complexity and prohibitive cost of CVD equipment makes it seldom available for undergraduate chemistry students. Here, a…

  4. Vertical Water Vapor Distribution at Phoenix

    NASA Astrophysics Data System (ADS)

    Tamppari, L. K.; Lemmon, M. T.

    2016-09-01

    The Phoenix SSI camera data along with radiative transfer modeling are used to retrieve the vertical water vapor profile. Preliminary results indicate that water vapor is often confined near the surface.

  5. Boiler for generating high quality vapor

    NASA Technical Reports Server (NTRS)

    Gray, V. H.; Marto, P. J.; Joslyn, A. W.

    1972-01-01

    Boiler supplies vapor for use in turbines by imparting a high angular velocity to the liquid annulus in heated rotating drum. Drum boiler provides a sharp interface between boiling liquid and vapor, thereby, inhibiting the formation of unwanted liquid droplets.

  6. Atomic vapor laser isotope separation process

    DOEpatents

    Wyeth, R.W.; Paisner, J.A.; Story, T.

    1990-08-21

    A laser spectroscopy system is utilized in an atomic vapor laser isotope separation process. The system determines spectral components of an atomic vapor utilizing a laser heterodyne technique. 23 figs.

  7. Speciation and temporal characterization of dicarboxylic acids in PM 2.5 during a PM episode and a period of non-episodic pollution

    NASA Astrophysics Data System (ADS)

    Hsieh, Li-Ying; Chen, Chien-Lung; Wan, Meng-Wei; Tsai, Cheng-Hsien; Tsai, Ying I.

    PM 2.5 aerosol was collected during a PM episode and a non-episodic pollution period between September and November 2004 in suburban southern Taiwan and dicarboxylic acid and inorganic species content and provenance were investigated. Oxalic acid was the dominant dicarboxylic acid species, followed by succinic acid and malonic acid. Tartaric acid concentrations were the lowest. There was 49.3% more dicarboxylic acid in PM episode aerosol than in non-episodic aerosol. However, daily oxalic acid concentration increased 72.7% in PM episode aerosol, while succinic acid fell 20.9% and malonic acid fell 21.6%, indicating higher conversion of these acids into oxalic acid in PM episode aerosol. Dicarboxylic acid concentrations, particularly oxalic acid, peaked at night during the PM episode, due to accumulation of daytime oxalic acid combined with low wind velocity and low mixing layer height at this time. SO 42-, NO 3- and NH 4+ were the dominant ionic species in both PM episode and non-episodic aerosols. NO 3- concentration increased 106% during the PM episode, while HNO 3, a gaseous precursor of NO 3-, fell 57%, indicating a large conversion of HNO 3 to aerosol phase NO 3- in PM episode aerosol. Backward trajectory data indicate that burning of paddy fields may also contribute to oxalic acid content in PM episode aerosol in the study area, especially during nighttime. Principal component analyses showed that succinic acid, malonic acid and oxalic acid were important factors in both pollution periods and also that there was high correlation between tartaric acid and NO x or HNO 2, indicative of vehicle emissions. The mass ratio of oxalic acid to sulfate in this aerosol was as high as 60.3‰, 35.5% higher than in non-episodic aerosol. Principal component analyses showed that photochemical aerosols contributed by succinic acid, malonic acid and oxalic acid were important factors in both periods. There was high correlation between tartaric acid and NO x or HNO 2

  8. Water Vapor Feedbacks to Climate Change

    NASA Technical Reports Server (NTRS)

    Rind, David

    1999-01-01

    The response of water vapor to climate change is investigated through a series of model studies with varying latitudinal temperature gradients, mean temperatures, and ultimately, actual climate change configurations. Questions to be addressed include: what role does varying convection have in water vapor feedback; do Hadley Circulation differences result in differences in water vapor in the upper troposphere; and, does increased eddy energy result in greater eddy vertical transport of water vapor in varying climate regimes?

  9. Vapor-Resistant Heat-Pipe Artery

    NASA Technical Reports Server (NTRS)

    Dussinger, Peter M.; Shaubach, Robert M.; Buchko, Matt

    1991-01-01

    Vapor lock in heat pipe delayed or prevented. Modifications of wick prevent flow of vapor into, or formation of vapor in, liquid-return artery. Small pores of fine-grained sintered wick help to prevent formation of large bubbles. Slotted tube offers few nucleation sites for bubbles. Improves return of liquid in heat pipe.

  10. 40 CFR 796.1950 - Vapor pressure.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 32 2011-07-01 2011-07-01 false Vapor pressure. 796.1950 Section 796... (CONTINUED) CHEMICAL FATE TESTING GUIDELINES Physical and Chemical Properties § 796.1950 Vapor pressure. (a... the vapor pressure of chemical and on environmental conditions which influence diffusion from...

  11. 40 CFR 796.1950 - Vapor pressure.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 32 2014-07-01 2014-07-01 false Vapor pressure. 796.1950 Section 796... (CONTINUED) CHEMICAL FATE TESTING GUIDELINES Physical and Chemical Properties § 796.1950 Vapor pressure. (a... the vapor pressure of chemical and on environmental conditions which influence diffusion from...

  12. 40 CFR 796.1950 - Vapor pressure.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 33 2012-07-01 2012-07-01 false Vapor pressure. 796.1950 Section 796... (CONTINUED) CHEMICAL FATE TESTING GUIDELINES Physical and Chemical Properties § 796.1950 Vapor pressure. (a... the vapor pressure of chemical and on environmental conditions which influence diffusion from...

  13. 40 CFR 796.1950 - Vapor pressure.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 33 2013-07-01 2013-07-01 false Vapor pressure. 796.1950 Section 796... (CONTINUED) CHEMICAL FATE TESTING GUIDELINES Physical and Chemical Properties § 796.1950 Vapor pressure. (a... the vapor pressure of chemical and on environmental conditions which influence diffusion from...

  14. Vapor Pressure Measurements in a Closed System

    ERIC Educational Resources Information Center

    Iannone, Mark

    2006-01-01

    An alternative method that uses a simple apparatus to measure vapor pressure versus temperature in a closed system, in which the total pressure is the vapor pressure of the liquid sample, is described. The use of this apparatus gives students a more direct picture of vapor pressure than the isoteniscope method and results have generally been quite…

  15. A colorimetric sensor array for detection of triacetone triperoxide vapor.

    PubMed

    Lin, Hengwei; Suslick, Kenneth S

    2010-11-10

    Triacetone triperoxide (TATP), one of the most dangerous primary explosives, has emerged as an explosive of choice for terrorists in recent years. Owing to the lack of UV absorbance, fluorescence, or facile ionization, TATP is extremely difficult to detect directly. Techniques that are able to detect generally require expensive instrumentation, need extensive sample preparation, or cannot detect TATP in the gas phase. Here we report a simple and highly sensitive colorimetric sensor for the detection of TATP vapor with semiquantitative analysis from 50 ppb to 10 ppm. By using a solid acid catalyst to pretreat a gas stream, we have discovered that a colorimetric sensor array of redox sensitive dyes can detect even very low levels of TATP vapor from its acid decomposition products (e.g., H(2)O(2)) with limits of detection (LOD) below 2 ppb (i.e., <0.02% of its saturation vapor pressure). Common potential interferences (e.g., humidity, personal hygiene products, perfume, laundry supplies, volatile organic compounds, etc.) do not generate an array response, and the array can also differentiate TATP from other chemical oxidants (e.g., hydrogen peroxide, bleach, tert-butylhydroperoxide, peracetic acid).

  16. Microwave-assisted fast vapor-phase transport synthesis of MnAPO-5 molecular sieves

    SciTech Connect

    Shao Hui; Yao Jianfeng; Ke Xuebin; Zhang Lixiong Xu Nanping

    2009-04-02

    MnAPO-5 was prepared by a microwave-assisted vapor-phase transport method at 180 deg. C in short times. The products were characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectra, UV-vis spectroscopic measurement, NH{sub 3}-temperature-programmed desorption and esterification reaction. It was found that dry gels prepared with aluminum isopropoxide, phosphoric acid and manganese acetate could be transferred to MnAPO-5 in the vapors of triethylamine and water by the microwave-assisted vapor-phase transport method at 180 deg. C for less than 30 min. The crystallization time was greatly reduced by the microwave heating compared with the conventional heating. The resulting MnAPO-5 exhibited much smaller particle sizes, higher surface areas and slightly higher catalytic activity in the esterification of acetic acid and butyl alcohol than those prepared by the conventional vapor-phase transport method and hydrothermal synthesis.

  17. Nitric Acid Uptake on Subtropical Cirrus Cloud Particles

    NASA Technical Reports Server (NTRS)

    Popp, P. J.; Gao, R. S.; Marcy, T. P.; Fahey, D. W.; Hudson, P. K.; Thompson, T. L.; Kaercher, B.; Ridley, B. A.; Weinheimer, A. J.; Knapp, D. J.; Montzka, D. D.; Baumgardner, D.; Garrett, T. J.; Weinstock, E. M.; Smith, J. B.; Sayres, D. S.; Pittman, J. V.; Dhaniyala, S.; Bui, T. P.; Mahoney, M. J.

    2004-01-01

    The redistribution of HNO3 via uptake and sedimentation by cirrus cloud particles is considered an important term in the upper tropospheric budget of reactive nitrogen. Numerous cirrus cloud encounters by the NASA WB-57F high-altitude research aircraft during the Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) were accompanied by the observation of condensed-phase HNO3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO3 with two independent channels of detection connected to separate forward and downward facing inlets that allow a determination of the amount of HNO3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO3 at temperatures of 197-224 K and pressures of 122-224 hPa. Maximum levels of condensed-phase HNO3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4 # 10(exp 14) molecules/ square cm were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO3 adsorption enthalpy of -11.0 kcal/mol, effectively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 ?m and particle fall velocities up to 10 m/s, some observed clouds have significant potential to redistribute HNO3 in the upper troposphere.

  18. Nitric Acid Uptake on Subtropical Cirrus Cloud Particles

    NASA Technical Reports Server (NTRS)

    2004-01-01

    The redistribution of HNO3 via uptake and sedimentation by cirrus cloud particles is considered an important term in the upper tropospheric budget of reactive nitrogen. Numerous cirrus cloud encounters by the NASA WB-57F high-altitude research aircraft during CRYSTAL-FACE were accompanied by the observation of condensed-phase HNO3 with the NOAA chemical ionization mass spectrometer. The instrument measures HNO3 with two independent channels of detection connected to separate forward- and downward-facing inlets that allow a determination of the amount of HNO3 condensed on ice particles. Subtropical cirrus clouds, as indicated by the presence of ice particles, were observed coincident with condensed-phase HNO3 at temperatures of 197 K - 224 K and pressures of 122 hPa - 224 hPa. Maximum levels of condensed-phase HNO3 approached the gas-phase equivalent of 0.8 ppbv. Ice particle surface coverages as high as 1.4- 10(exp 14) molecules/sq cm were observed. A dissociative Langmuir adsorption model, when using an empirically derived HNO3 adsorption enthalpy of -11.0 kcal/mol, effectively describes the observed molecular coverages to within a factor of 5. The percentage of total HNO3 in the condensed phase ranged from near zero to 100% in the observed cirrus clouds. With volume-weighted mean particle diameters up to 700 pm and particle fall velocities up to 10 m/s, some observed clouds have significant potential to redistribute HNO3 in the upper troposphere.

  19. Production of higher quality bio-oils by in-line esterification of pyrolysis vapor

    SciTech Connect

    Hilten, Roger Norris; Das, Keshav; Kastner, James R; Bibens, Brian P

    2014-12-02

    The disclosure encompasses in-line reactive condensation processes via vapor phase esterification of bio-oil to decease reactive species concentration and water content in the oily phase of a two-phase oil, thereby increasing storage stability and heating value. Esterification of the bio-oil vapor occurs via the vapor phase contact and subsequent reaction of organic acids with ethanol during condensation results in the production of water and esters. The pyrolysis oil product can have an increased ester content and an increased stability when compared to a condensed pyrolysis oil product not treated with an atomized alcohol.

  20. Evaporation rates and vapor pressures of individual aerosol species formed in the atmospheric oxidation of alpha- and beta-pinene.

    PubMed

    Bilde, M; Pandis, S N

    2001-08-15

    The semivolatile oxidation products (trans-norpinic acid, pinic acid, cis-pinonic acid, etc.) of the biogenic monoterpenes (alpha-pinene, beta-pinene, etc.) contribute to the atmospheric burden of particulate matter. Using the tandem differential mobility analysis (TDMA) technique evaporation rates of glutaric acid, trans-norpinic acid, and pinic acid particles were measured in a laminar flow reactor. The vapor pressure of glutaric acid was found to be log(p0 glutaric/Pa) = - 3,510 K/T + 8.647 over the temperature range 290-300 K in good agreement with the values previously reported by Tao and McMurry (1989). The measured vapor pressure of trans-norpinic acid over the temperature range 290-312 K is log(p0 norpinic/Pa) = - 2,196.9 K/T + 3.522, and the vapor pressure of pinic acid is log(p0 pinic/ Pa) = - 5,691.7 K/T + 14.73 over the temperature range 290-323 K. The uncertainty on the reported vapor pressures is estimated to be approximately +/- 50%. The vapor pressure of cis-pinonic acid is estimated to be of the order of 7 x 10(-5) Pa at 296 K.

  1. Effects of inorganic acids and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process.

    PubMed

    Zhang, Jian; Xia, Yuguo; Zhang, Li; Chen, Dairong; Jiao, Xiuling

    2015-11-07

    In-depth understanding of the sol-gel process plays an essential role in guiding the preparation of new materials. Herein, the effects of different inorganic acids (HCl, HNO3 and H2SO4) and divalent hydrated metal cations (Mg(2+), Ca(2+), Co(2+), Ni(2+)) on γ-AlOOH sol-gel process were studied based on experiments and density functional theory (DFT) calculations. In these experiments, the sol originating from the γ-AlOOH suspension was formed only with the addition of HCl and HNO3, but not with H2SO4. Furthermore, the DFT calculations showed that the strong adsorption of HSO4(-) on the surface of the γ-AlOOH particles, and the hydrogen in HSO4(-) pointing towards the solvent lead to an unstable configuration of electric double layer (EDL). In the experiment, the gelation time sequence of γ-AlOOH sol obtained by adding metal ions changed when the ionic strength was equal to or greater than 0.198 mol kg(-1). The DFT calculations demonstrated that the adsorption energy of hydrated metal ions on the γ-AlOOH surface can actually make a difference in the sol-gel process.

  2. The effect of heating temperature and nitric acid treatments on the performance of Cu- and Zn-based broad spectrum respirator carbons.

    PubMed

    Smith, J W H; Romero, J V; Dahn, T R; Dunphy, K; Sullivan, B; Mallay, M; Croll, L M; Reynolds, J H; Andress, C; Dahn, J R

    2011-12-01

    Impregnated activated carbons (IACs) that are used in broad spectrum gas mask applications have historically contained copper and/or zinc impregnants. The addition of an oxidizing agent, such as nitric acid (HNO(3)) can be useful in distributing the metallic impregnants uniformly on the activated carbon substrate. In this work, we study IACs prepared from copper nitrate (Cu(NO(3))(2)) and zinc nitrate (Zn(NO(3))(2)) precursors as a function of HNO(3) content present in the impregnating solution and as a function of heating temperature. The gas adsorption capacity of the IACs was determined by dynamic flow testing using sulfur dioxide (SO(2)), ammonia (NH(3)), hydrogen cyanide (HCN) and cyclohexane (C(6)H(12)) challenge gases under dry and humid conditions. The thermal decomposition and distribution of the impregnant on the activated carbon substrate is studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermal analysis techniques. Relationships between gas adsorption capacity, impregnant distribution and the species of surface impregnants are discussed.

  3. Preliminary measurements of summer nitric acid and ammonia concentrations in the Lake Tahoe Basin air-shed: implications for dry deposition of atmospheric nitrogen.

    PubMed

    Tarnay, L; Gertler, A W; Blank, R R; Taylor, G E

    2001-01-01

    Over the past 50 years, Lake Tahoe, an alpine lake located in the Sierra Nevada mountains on the border between California and Nevada, has seen a decline in water clarity. With significant urbanization within its borders and major urban areas 130 km upwind of the prevailing synoptic airflow, it is believed the Lake Tahoe Basin is receiving substantial nitrogen (N) input via atmospheric deposition during summer and fall. We present preliminary inferential flux estimates to both lake surface and forest canopy based on empirical measurements of ambient nitric acid (HNO3), ammonia (NH3), and ammonium nitrate (NH4NO3) concentrations, in an effort to identify the major contributors to and ranges of atmospheric dry N deposition to the Lake Tahoe Basin. Total flux from dry deposition ranges from 1.2 to 8.6 kg N ha-1 for the summer and fall dry season and is significantly higher than wet deposition, which ranges from 1.7 to 2.9 kg N ha-1 year-1. These preliminary results suggest that dry deposition of HNO3 is the major source of atmospheric N deposition for the Lake Tahoe Basin, and that overall N deposition is similar in magnitude to deposition reported for sites exposed to moderate N pollution in the southern California mountains.

  4. Adsorption and separation behavior of yttrium and strontium in nitric acid solution by extraction chromatography using a macroporous silica-based adsorbent.

    PubMed

    Xu, Yuanlai; Kim, Seong-Yun; Ito, Tatsuya; Nakazawa, Kasane; Funaki, Yoshihito; Tada, Tsutomu; Hitomi, Keitaro; Ishii, Keizo

    2012-11-09

    To separate (90)Y from the fission product (90)Sr-(90)Y group, a silica-based TODGA/SiO(2)-P adsorbent was prepared by impregnating N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) extractant into the macroporous SiO(2)-P support with a mean diameter of 60 μm. The adsorption behavior of Sr(II) and Y(III) onto TODGA/SiO(2)-P adsorbent from HNO(3) solution and their mutual separation were investigated. Under the experimental conditions, this adsorbent showed high adsorption affinity to Y(III) and weak adsorption to Sr(II). It was found that the adsorption process of Y(III) could be expressed by both of Langmuir monomolecular layer adsorption mode and the pseudo-second order model. From the results of stability experiments, it became clear that TODGA/SiO(2)-P adsorbent is stable in 3M HNO(3) solution for 1 month contact time at 298 K. Using a column packed with TODGA/SiO(2)-P adsorbent, Sr(II) and Y(III) were eluted by distilled water and diethylenetriamine pentaacetic acid (DTPA) solution, respectively. The separation of Y(III) from Sr(II)-Y(III) group was achieved successfully.

  5. Measurements of Acidic Gases and Aerosol Species Aboard the NASA DC-8 Aircraft During the Pacific Exploratory Mission in the Tropics (PEM-Tropics A)

    NASA Technical Reports Server (NTRS)

    Talbot, Robert W.; Dibb, Jack E.

    1999-01-01

    We received funding to provide measurements of nitric acid (HNO3), formic acid (HCOOH), acetic acid (CH3COOH), and the chemical composition of aerosols aboard the NASA Ames DC-8 research aircraft during the PEM-Tropics A mission. These measurements were successfully completed and the final data resides in the electronic archive (ftp-gte.larc.nasa.gov) at NASA Langley Research Center. For the PEM-Tropics A mission the University of New Hampshire group was first author of four different manuscripts. Three of these have now appeared in the Journal of Geophysical Research-Atmospheres, included in the two section sections on PEM-Tropics A. The fourth manuscript has just recently been submitted to this same journal as a stand alone paper. All four of these papers are included in this report. The first paper (Influence of biomass combustion emissions on the distribution of acidic trace gases over the Southern Pacific basin during austral springtime) describes the large-scale distributions of HNO3, HCOOH, and CH3COOH. Arguments were presented to show, particularly in the middle tropospheric region, that biomass burning emissions from South America and Africa were a major source of acidic gases over the South Pacific basin. The second paper (Aerosol chemical composition and distribution during the Pacific Exploratory Mission (PEM) Tropics) covers the aerosol aspects of our measurement package. Compared to acidic gases, O3, and selected hydrocarbons, the aerosol chemistry showed little influence from biomass burning emissions. The data collected in the marine boundary layer showed a possible marine source of NH3 to the troposphere in equatorial areas. This source had been speculated on previously, but our data was the first collected from an airborne platform to show its large-scale features. The third paper (Constraints on the age and dilution of Pacific Exploratory Mission-Tropics biomass burning plumes from the natural radionuclide tracer Pb-210) utilized the unexpectedly

  6. The effects of acid leaching on 40Ar/39Ar age dating results using samples from the Walvis Ridge hotspot trail

    NASA Astrophysics Data System (ADS)

    Klath, J. F.; Koppers, A. A.; Heaton, D. E.; Schnur, S.

    2013-12-01

    In this study we systematically explore how acid leaching can be used to reduce the negative effects of seawater alteration on the 40Ar/39Ar age dating of submarine basalts. Koppers et al (2000) showed that acid leaching of groundmass samples generated more consistent ages as well as ages more concordant with phenocrystic mineral phases, compared to samples that were left untreated. By studying the effects of progressively increasing the strength and length of acid treatment, we will show how acid leaching of groundmass separates reduces alteration while leaving the initial eruption signature intact. Samples were chosen from the Walvis ridge hotspot trail in the southeast Atlantic. Three samples were selected based on degree and style of alteration. Two samples (basalt and basaltic andesite) appear highly altered in thin section. The basalt contains diffuse iddingsite alteration that is pervasive throughout the groundmass. The basaltic andesite displays focused secondary mineral phases within and around abundant vesicles. The third sample, a trachyte, shows relatively minor degrees of alteration in thin section. These groundmass separates were divided into four splits and treated with a progressively stronger acid and for longer duration. One split from each rock was left untreated to act as a baseline. Of the other three splits from each sample, one was treated with a mild leach (1N HCl and 1N HNO3), one a strong leach (1N HCl, 1N HNO3, 6N HCl, and 3N HNO3), and lastly the strong leach performed twice. The samples were then handpicked to remove any remaining visible alteration. The untreated samples were picked as well, removing the most distinctly altered grains. All splits were analyzed by electron microprobe, x-ray fluorescence (XRF) and the incremental heating 40Ar/39Ar dating method. We will report on the results of an image analysis of microprobe backscatter images and elemental maps taken of individual groundmass grains. This analysis will show the location

  7. Vapor deposition of tantalum and tantalum compounds

    SciTech Connect

    Trkula, M.

    1996-04-01

    Tantalum, and many of its compounds, can be deposited as coatings with techniques ranging from pure, thermal chemical vapor deposition to pure physical vapor deposition. This review concentrates on chemical vapor deposition techniques. The paper takes a historical approach. The authors review classical, metal halide-based techniques and current techniques for tantalum chemical vapor deposition. The advantages and limitations of the techniques will be compared. The need for new lower temperature processes and hence new precursor chemicals will be examined and explained. In the last section, they add some speculation as to possible new, low-temperature precursors for tantalum chemical vapor deposition.

  8. What Good is Raman Water Vapor Lidar?

    NASA Technical Reports Server (NTRS)

    Whitman, David

    2011-01-01

    Raman lidar has been used to quantify water vapor in the atmosphere for various scientific studies including mesoscale meteorology and satellite validation. Now the international networks of NDACC and GRUAN have interest in using Raman water vapor lidar for detecting trends in atmospheric water vapor concentrations. What are the data needs for addressing these very different measurement challenges. We will review briefly the scientific needs for water vapor accuracy for each of these three applications and attempt to translate that into performance specifications for Raman lidar in an effort to address the question in the title of "What good is Raman water vapor Iidar."

  9. Active Hydrazine Vapor Sampler (AHVS)

    NASA Technical Reports Server (NTRS)

    Young, Rebecca C.; Mcbrearty, Charles F.; Curran, Daniel J.

    1993-01-01

    The Active Hydrazine Vapor Sampler (AHVS) was developed to detect vapors of hydrazine (HZ) and monomethylhydrazine (MMH) in air at parts-per-billion (ppb) concentration levels. The sampler consists of a commercial personal pump that draws ambient air through paper tape treated with vanillin (4-hydroxy-3-methoxybenzaldehyde). The paper tape is sandwiched in a thin cardboard housing inserted in one of the two specially designed holders to facilitate sampling. Contaminated air reacts with vanillin to develop a yellow color. The density of the color is proportional to the concentration of HZ or MMH. The AHVS can detect 10 ppb in less than 5 minutes. The sampler is easy to use, low cost, and intrinsically safe and contains no toxic material. It is most beneficial for use in locations with no laboratory capabilities for instrumentation calibration. This paper reviews the development, laboratory test, and field test of the device.

  10. Vaporization chambers and associated methods

    DOEpatents

    Turner, Terry D.; Wilding, Bruce M.; McKellar, Michael G.; Shunn, Lee P.

    2017-02-21

    A vaporization chamber may include at least one conduit and a shell. The at least one conduit may have an inlet at a first end, an outlet at a second end and a flow path therebetween. The shell may surround a portion of each conduit and define a chamber surrounding the portion of each conduit. Additionally, a plurality of discrete apertures may be positioned at longitudinal intervals in a wall of each conduit, each discrete aperture of the plurality of discrete apertures sized and configured to direct a jet of fluid into each conduit from the chamber. A liquid may be vaporized by directing a first fluid comprising a liquid into the inlet at the first end of each conduit, directing jets of a second fluid into each conduit from the chamber through discrete apertures in a wall of each conduit and transferring heat from the second fluid to the first fluid.

  11. SWAS observations of water vapor in the Venus mesosphere

    NASA Astrophysics Data System (ADS)

    Gurwell, Mark A.; Melnick, Gary J.; Tolls, Volker; Bergin, Edwin A.; Patten, Brian M.

    2007-06-01

    variability on time scales of less than a week was not detected. The mesospheric water vapor is expected to be in equilibrium with aerosol particles, primarily composed of concentrated sulfuric acid, in the upper haze layers of the Venus atmosphere. If true, moderate amplitude (10-15 K) variability in mesospheric temperature, previously noted in millimeter spectroscopy observations of Venus, can explain the rapid water vapor variability detected by SWAS.

  12. Chemical vapor deposition of sialon

    DOEpatents

    Landingham, R.L.; Casey, A.W.

    A laminated composite and a method for forming the composite by chemical vapor deposition are described. The composite includes a layer of sialon and a material to which the layer is bonded. The method includes the steps of exposing a surface of the material to an ammonia containing atmosphere; heating the surface to at least about 1200/sup 0/C; and impinging a gas containing N/sub 2/, SiCl/sub 4/, and AlCl/sub 3/ on the surface.

  13. Internal Water Vapor Photoacoustic Calibration

    NASA Technical Reports Server (NTRS)

    Pilgrim, Jeffrey S.

    2009-01-01

    Water vapor absorption is ubiquitous in the infrared wavelength range where photoacoustic trace gas detectors operate. This technique allows for discontinuous wavelength tuning by temperature-jumping a laser diode from one range to another within a time span suitable for photoacoustic calibration. The use of an internal calibration eliminates the need for external calibrated reference gases. Commercial applications include an improvement of photoacoustic spectrometers in all fields of use.

  14. Evaporation by mechanical vapor recompression

    NASA Astrophysics Data System (ADS)

    Iverson, C. H.; Coury, G. E.

    1980-04-01

    Progress in the development of a study of the application of the technologies of mechanical vapor recompression and falling film evaporation as applied to the beet sugar industry is reported. Progress is reported in the following areas: technical literature search; report on visit to European factories using these technologies; energy balance studies of factories offered by the industry as candidates for the demonstration plants; and report on energy balance studies and the recommendations as to the site for the demonstration plant.

  15. Vaporization Would Cool Primary Battery

    NASA Technical Reports Server (NTRS)

    Bhandari, Pradeep; Miyake, Robert N.

    1991-01-01

    Temperature of discharging high-power-density primary battery maintained below specified level by evaporation of suitable liquid from jacket surrounding battery, according to proposal. Pressure-relief valve regulates pressure and boiling temperature of liquid. Less material needed in cooling by vaporization than in cooling by melting. Technique used to cool batteries in situations in which engineering constraints on volume, mass, and location prevent attachment of cooling fins, heat pipes, or like.

  16. Studies on Vapor Adsorption Systems

    NASA Technical Reports Server (NTRS)

    Shamsundar, N.; Ramotowski, M.

    1998-01-01

    The project consisted of performing experiments on single and dual bed vapor adsorption systems, thermodynamic cycle optimization, and thermal modeling. The work was described in a technical paper that appeared in conference proceedings and a Master's thesis, which were previously submitted to NASA. The present report describes some additional thermal modeling work done subsequently, and includes listings of computer codes developed during the project. Recommendations for future work are provided.

  17. A novel chemically selective siloxane polymer for chemical vapor sensing

    NASA Astrophysics Data System (ADS)

    Huang, Jia; Jiang, Yadong; Du, Xiaosong; Bi, Juan

    2010-10-01

    A new hydrogen-bond acidic carbosiloxane polymer for quartz crystal microbalance sensors (QCMs) application was synthesized via O-alkylation, Claisen rearrange, hydrosilylation reaction and functionalized the polysiloxane with trifluoroacetone groups (TFA). The trifluoroisopropanol functionalized polysiloxane was characterized by FT-IR and 1HNMR. And this novel siloxane polymer was coated onto AT-cut 8 MHz QCM sensors to investigate its gas sensitive responses to the organophosphorus nerve agent stimulant dimethyl methylphosphonate (DMMP) vapor as well as other interfering organic vapors. The research work indicated that frequency shifts of the trifluoroisopropanol functionalized polysiloxane based QCM sensor to the DMMP vapor were completely linear, and with a regression coefficient of 0.9973 in the concentration range of 10-60 ppm. In addition, the sensitivity of the fabricated QCM sensors to DMMP was up to 10.64 Hz/ ppm, and much higher than the other interfering vapors, limits of detection (LODs) of the QCM sensors was 0.28 ppm, thus high selectivity to DMMP was demonstrated in this work.

  18. Means and method for vapor generation

    DOEpatents

    Carlson, L.W.

    A liquid, in heat transfer contact with a surface heated to a temperature well above the vaporization temperature of the liquid, will undergo a multiphase (liquid-vapor) transformation from 0% vapor to 100% vapor. During this transition, the temperature driving force or heat flux and the coefficients of heat transfer across the fluid-solid interface, and the vapor percentage influence the type of heating of the fluid - starting as feedwater heating where no vapors are present, progressing to nucleate heating where vaporization begins and some vapors are present, and concluding with film heating where only vapors are present. Unstable heating between nucleate and film heating can occur, accompanied by possibly large and rapid temperature shifts in the structures. This invention provides for injecting into the region of potential unstable heating and proximate the heated surface superheated vapors in sufficient quantities operable to rapidly increase the vapor percentage of the multiphase mixture by perhaps 10 to 30% and thereby effectively shift the multiphase mixture beyond the unstable heating region and up to the stable film heating region.

  19. Means and method for vapor generation

    DOEpatents

    Carlson, Larry W.

    1984-01-01

    A liquid, in heat transfer contact with a surface heated to a temperature well above the vaporization temperature of the liquid, will undergo a multiphase (liquid-vapor) transformation from 0% vapor to 100% vapor. During this transition, the temperature driving force or heat flux and the coefficients of heat transfer across the fluid-solid interface, and the vapor percentage influence the type of heating of the fluid--starting as "feedwater" heating where no vapors are present, progressing to "nucleate" heating where vaporization begins and some vapors are present, and concluding with "film" heating where only vapors are present. Unstable heating between nucleate and film heating can occur, accompanied by possibly large and rapid temperature shifts in the structures. This invention provides for injecting into the region of potential unstable heating and proximate the heated surface superheated vapors in sufficient quantities operable to rapidly increase the vapor percentage of the multiphase mixture by perhaps 10-30% and thereby effectively shift the multiphase mixture beyond the unstable heating region and up to the stable film heating region.

  20. Critical points of metal vapors

    SciTech Connect

    Khomkin, A. L. Shumikhin, A. S.

    2015-09-15

    A new method is proposed for calculating the parameters of critical points and binodals for the vapor–liquid (insulator–metal) phase transition in vapors of metals with multielectron valence shells. The method is based on a model developed earlier for the vapors of alkali metals, atomic hydrogen, and exciton gas, proceeding from the assumption that the cohesion determining the basic characteristics of metals under normal conditions is also responsible for their properties in the vicinity of the critical point. It is proposed to calculate the cohesion of multielectron atoms using well-known scaling relations for the binding energy, which are constructed for most metals in the periodic table by processing the results of many numerical calculations. The adopted model allows the parameters of critical points and binodals for the vapor–liquid phase transition in metal vapors to be calculated using published data on the properties of metals under normal conditions. The parameters of critical points have been calculated for a large number of metals and show satisfactory agreement with experimental data for alkali metals and with available estimates for all other metals. Binodals of metals have been calculated for the first time.

  1. Acoustic Droplet Vaporization in Microchannels

    NASA Astrophysics Data System (ADS)

    Li, David; Fabiilli, Mario; Kripfgans, Oliver; Fowlkes, J. Brian; Bull, Joseph

    2014-11-01

    Gas embolotherapy is a proposed cancer therapy where gas bubbles acting as embolic agents are selectively generated near the tumor site to block blood supply, resulting to tumor necrosis. The gas bubbles are generated by using focused ultrasound to selective vaporize intravenously injected microdroplets. In this study, albumin encapsulated dodecafluorocarbon microdroplets were isolated in 25 to 100 micron diameter polydimethylsiloxane microchannels. The droplets were vaporized at 37 °C using a single pulse from a 7.5 MHz single element focused transducer with 8-32 cycles at 2.2 to 5.6 MPa peak negative pressure. The vaporization process was recorded using an ultra-high speed camera attached to an inverted microscope. A theoretical Rayleigh-Plesset like model was derived to describe the both the expansion of small spherical bubbles as well as cylindrical bubbles in a long microchannel. The gas phase was described as an ideal gas and the liquid DDFP and bulk fluid were viscous Newtonian fluids. Additionally, surface tension, viscous losses from the channel, and the phase change process were included in the model. The theoretical model matched very well to experiments with channel diameters or 50 micron or less. This work was supported by NIH Grant R01EB006476.

  2. Water vapor diffusion membrane development

    NASA Technical Reports Server (NTRS)

    Tan, M. K.

    1977-01-01

    An application of the water vapor diffusion technique is examined whereby the permeated water vapor is vented to space vacuum to alleviate on-board waste storage and provide supplemental cooling. The work reported herein deals primarily with the vapor diffusion-heat rejection (VD-HR) as it applies to the Space Shuttle. A stack configuration was selected, designed and fabricated. An asymmetric cellulose acetate membrane, used in reverse osmosis application was selected and a special spacer was designed to enhance mixing and promote mass transfer. A skid-mount unit was assembled from components used in the bench unit although no attempt was made to render it flight-suitable. The operating conditions of the VD-HR were examined and defined and a 60-day continuous test was carried out. The membranes performed very well throughout the test; no membrane rupture and no unusual flux decay was observed. In addition, a tentative design for a flight-suitable VD-HR unit was made.

  3. Vapor pressure of water nanodroplets.

    PubMed

    Factorovich, Matías H; Molinero, Valeria; Scherlis, Damián A

    2014-03-26

    Classical thermodynamics is assumed to be valid up to a certain length-scale, below which the discontinuous nature of matter becomes manifest. In particular, this must be the case for the description of the vapor pressure based on the Kelvin equation. However, the legitimacy of this equation in the nanoscopic regime can not be simply established, because the determination of the vapor pressure of very small droplets poses a challenge both for experiments and simulations. In this article we make use of a grand canonical screening approach recently proposed to compute the vapor pressures of finite systems from molecular dynamics simulations. This scheme is applied to water droplets, to show that the applicability of the Kelvin equation extends to unexpectedly small lengths, of only 1 nm, where the inhomogeneities in the density of matter occur within spatial lengths of the same order of magnitude as the size of the object. While in principle this appears to violate the main assumptions underlying thermodynamics, the density profiles reveal, however, that structures of this size are still homogeneous in the nanosecond time-scale. Only when the inhomogeneity in the density persists through the temporal average, as it is the case for clusters of 40 particles or less, do the macroscopic thermodynamics and the molecular descriptions depart from each other.

  4. Interaction of aerosol particles composed of protein and salts with water vapor: hygroscopic growth and microstructural rearrangement

    NASA Astrophysics Data System (ADS)

    Mikhailov, E.; Vlasenko, S.; Niessner, R.; Pöschl, U.

    2003-09-01

    decomposition products NH3 and HNO3. The efflorescence threshold of NaCl-BSA particles decreased with increasing BSA dry mass fraction, i.e. the protein inhibited the formation of salt crystals and enhanced the stability of supersaturated solution droplets. The H-TDMA and TEM results indicate that the protein was enriched at the surface of the mixed particles and formed an envelope, which inhibits the access of water vapor to the particle core and leads to kinetic limitations of hygroscopic growth, phase transitions, and microstructural rearrangement processes. Besides these surface and kinetic effects, proteins and comparable organic macromolecules may also influence the thermodynamic properties of the aqueous bulk solution (solubilities, vapor pressures, and chemical equilibria, e.g. for the decomposition and evaporation of NH4NO3. The observed effects should be taken into account in the analysis of data from laboratory experiments and field measurements and in the modelling of aerosol processes involving water vapor and particles with complex composition. They can strongly influence experimental results, and depending on ambient conditions they may also play a significant role in the atmosphere (deliquescence, efflorescence, and CCN activation of particles). In fact, irregular hygroscopic growth curves similar to the ones observed in this study have recently been reported from H-TDMA experiments with water-soluble organics extracted from real air particulate matter and with humic-like substances. The Köhler theory calculations performed with different models demonstrate that the hygroscopic growth of particles composed of inorganic salts and proteins can be efficiently described with a simple volume additivity approach, provided that the correct dry solute mass equivalent diameter and composition are known. A simple parameterisation of the osmotic coefficient has been derived from an osmotic pressure virial equation and appears to be well-suited for proteins and comparable

  5. Laboratory simulations of NAT formation approaching stratospheric conditions

    NASA Technical Reports Server (NTRS)

    Marti, James; Mauersberger, Konrad

    1994-01-01

    Previous laboratory studies have established the stability conditions of nitric acid trihydrate (NAT), of which type 1 polar stratospheric cloud (PSC 1) particles are thought to be composed. However, NAT samples in lab studies were almost always formed under conditions very different from those of the stratosphere. In order to better understand the in situ growth of PSC 1 particle populations, samples of water and nitric acid were deposited under conditions of temperature and pressure which more closely approximate the polar stratosphere. The compositions of the solids, measured shortly after deposition, depended on the H2O:HNO3 ratio in the vapor from which the solids were condensed. Solids formed from vapor mixtures that approached stratospheric contained significantly less HNO3 than the 25 mol percent expected of NAT.

  6. Stratospheric Sulfuric Acid and Black Carbon Aerosol Measured During POLARIS and its Role in Ozone Chemistry

    NASA Technical Reports Server (NTRS)

    Strawa, Anthony W.; Pueschel, R. F.; Drdla, K.; Verma, S.; Gore, Warren J. (Technical Monitor)

    1998-01-01

    Stratospheric aerosol can affect the environment in three ways. Sulfuric acid aerosol have been shown to act as sites for the reduction of reactive nitrogen and chlorine and as condensation sites to form Polar Stratospheric Clouds, under very cold conditions, which facilitate ozone depletion. Recently, modeling studies have suggested a link between BCA (Black Carbon Aerosol) and ozone chemistry. These studies suggest that HNO3, NO2, and O3 may be reduced heterogeneously on BCA particles. The ozone reaction converts ozone to oxygen molecules, while HNO3 and NO2 react to form NOx. Finally, a buildup of BCA could reduce the single-scatter albedo of aerosol below a value of 0.98, a critical value that has been postulated to change the effect of stratospheric aerosol from cooling to warming. Correlations between measured BCA amounts and aircraft usage have been reported. Attempts to link BCA to ozone chemistry and other stratospheric processes have been hindered by questions concerning the amount of BCA that exists in the stratosphere, the magnitude of reaction probabilities, and the scarcity of BCA measurements. The Ames Wire Impactors (AWI) participated in POLARIS as part of the complement of experiments on the NASA ER-2. One of our main objectives was to determine the amount of aerosol surface area, particularly BCA, available for reaction with stratospheric constituents and assess if possible, the importance of these reactions. The AWI collects aerosol and BCA particles on thin Palladium wires that are exposed to the ambient air in a controlled manner. The samples are returned to the laboratory for subsequent analysis. The product of the AWI analysis is the size, surface area, and volume distributions, morphology and elemental composition of aerosol and BCA. This paper presents results from our experiments during POLARIS and puts these measurements in the context of POLARIS and other missions in which we have participated. It describes modifications to the AWI data

  7. Laboratory Investigations of Heterogeneous Chemistry Important to Ozone Depletion in the Stratosphere

    NASA Astrophysics Data System (ADS)

    Zhang, Renyi

    Results of laboratory investigations of heterogeneous chemistry important to ozone depletion in the stratosphere are presented. Thermodynamic properties (such as melting points, enthalpies of fusion, etc.) for acids which are present in the stratosphere (HCl, HNO_3 , and H_2SO_4 ) are studied using laboratory-assembled apparatus of electrical conductivity and differential thermal analysis and using a commercial differential scanning calorimeter (DSC). Vapor pressures and infrared spectra of liquid and supercooled solutions, and of liquid-solid and solid -solid coexistence mixtures for the HCl/H_2 O and H_2SO_4 /H_2O binary systems are investigated. Equilibrium constants and standard enthalpies of formation for the pure crystalline hydrates of those acids as well as their corresponding liquid compositions are determined from the vapor pressure and calorimetric data. A theoretical approach, which allows determination of vapor pressures for two adjacent hydrates in thermodynamic equilibrium and for the coexistence systems involving a hydrate and ice in a binary system, is presented in terms of chemical equilibrium principles and compared with the experimental data for thermodynamic consistence. Vapor pressures of HNO_3 and HCl over H_2SO_4 /HNO_3/H_2 O and H_2SO_4 /HCl/H_2O solutions as well as over H_2SO_4/HNO _3/HCl/H_2O solutions are also measured in order to predict incorporation of stratospheric acids into the background sulfate aerosols. From the data, the Henry's law solubility constants for those systems are determined and the equilibrium compositions of aqueous stratospheric aerosols are predicted as a function of ambient temperature and mixing ratios of H_2 O and HNO_3. The results indicate that at the low temperatures characteristic of the stratosphere at high latitudes in the winter and spring, the HNO_3 content reaches levels of the order of 10% wt in the background sulfate aerosols. The results also reveal that the amount of dissolved HCl in the

  8. Vaporization modeling of petroleum-biofuel drops using a hybrid multi-component approach

    SciTech Connect

    Zhang, Lei; Kong, Song-Charng

    2010-11-15

    Numerical modeling of the vaporization characteristics of multi-component fuel mixtures is performed in this study. The fuel mixtures studied include those of binary components, biodiesel, diesel-biodiesel, and gasoline-ethanol. The use of biofuels has become increasingly important for reasons of environmental sustainability. Biofuels are often blended with petroleum fuels, and the detailed understanding of the vaporization process is essential to designing a clean and efficient combustion system. In this study, a hybrid vaporization model is developed that uses continuous thermodynamics to describe petroleum fuels and discrete components to represent biofuels. The model is validated using the experimental data of n-heptane, n-heptane-n-decane mixture, and biodiesel. Since biodiesel properties are not universal due to the variation in feedstock, methods for predicting biodiesel properties based on the five dominant fatty acid components are introduced. Good levels of agreement in the predicted and measured drop size histories are obtained. Furthermore, in modeling the diesel-biodiesel drop, results show that the drop lifetime increases with the biodiesel concentration in the blend. During vaporization, only the lighter components of diesel fuel vaporize at the beginning. Biodiesel components do not vaporize until some time during the vaporization process. On the other hand, results of gasoline-ethanol drops indicate that both fuels start to vaporize once the process begins. At the beginning, the lighter components of gasoline have a slightly higher vaporization rate than ethanol. After a certain time, ethanol vaporizes faster than the remaining gasoline components. At the end, the drop reduces to a regular gasoline drop with heavier components. Overall, the drop lifetime increases as the concentration of ethanol increases in the drop due to the higher latent heat. (author)

  9. Process for recovering organic vapors from air

    DOEpatents

    Baker, Richard W.

    1985-01-01

    A process for recovering and concentrating organic vapor from a feed stream of air having an organic vapor content of no more than 20,000 ppm by volume. A thin semipermeable membrane is provided which has a feed side and a permeate side, a selectivity for organic vapor over air of at least 50, as measured by the ratio of organic vapor permeability to nitrogen permeability, and a permeability of organic vapor of at least 3.times.10.sup.-7 cm.sup.3 (STP) cm/cm.sup.2 sec.cm Hg. The feed stream is passed across the feed side of the thin semipermeable membrane while providing a pressure on the permeate side which is lower than the feed side by creating a partial vacuum on the permeate side so that organic vapor passes preferentially through the membrane to form an organic vapor depleted air stream on the feed side and an organic vapor enriched stream on the permeate side. The organic vapor which has passed through the membrane is compressed and condensed to recover the vapor as a liquid.

  10. Vapors-liquid phase separator

    NASA Astrophysics Data System (ADS)

    Frederking, T. H. K.; Brown, G. S.; Chuang, C.; Kamioka, Y.; Kim, Y. I.; Lee, J. M.; Yuan, S. W. K.

    1980-10-01

    The use of porous plugs, mostly with in the form of passive devices with constant area were considered as vapor-liquid phase separators for helium 2 storage vessels under reduced gravity. The incorporation of components with variable cross sectional area as a method of flow rate modification was also investigated. A particular device which uses a shutter-type system for area variation was designed and constructed. This system successfully permitted flor rate changes of up to plus or minus 60% from its mean value.

  11. Water vapor diffusion membrane development

    NASA Technical Reports Server (NTRS)

    Tan, M. K.

    1976-01-01

    A total of 18 different membranes were procured, characterized, and tested in a modified bench-scale vapor diffusion water reclamation unit. Four membranes were selected for further studies involving membrane fouling. Emphasis was placed on the problem of flux decline due to membrane fouling. This is discussed in greater details under "Summary and Discussion on Membrane Fouling Studies" presented in pages 47-51. The system was also investigated for low temperature application on wash-water where the permeated water is not recovered but vented into space vacuum.

  12. Advanced Raman water vapor lidar

    NASA Technical Reports Server (NTRS)

    Whiteman, David N.; Melfi, S. Harvey; Ferrare, Richard A.; Evans, Keith A.; Ramos-Izquierdo, Luis; Staley, O. Glenn; Disilvestre, Raymond W.; Gorin, Inna; Kirks, Kenneth R.; Mamakos, William A.

    1992-01-01

    Water vapor and aerosols are important atmospheric constituents. Knowledge of the structure of water vapor is important in understanding convective development, atmospheric stability, the interaction of the atmosphere with the surface, and energy feedback mechanisms and how they relate to global warming calculations. The Raman Lidar group at the NASA Goddard Space Flight Center (GSFC) developed an advanced Raman Lidar for use in measuring water vapor and aerosols in the earth's atmosphere. Drawing on the experience gained through the development and use of our previous Nd:YAG based system, we have developed a completely new lidar system which uses a XeF excimer laser and a large scanning mirror. The additional power of the excimer and the considerably improved optical throughput of the system have resulted in approximately a factor of 25 improvement in system performance for nighttime measurements. Every component of the current system has new design concepts incorporated. The lidar system consists of two mobile trailers; the first (13m x 2.4m) houses the lidar instrument, the other (9.75m x 2.4m) is for system control, realtime data display, and analysis. The laser transmitter is a Lambda Physik LPX 240 iCC operating at 400 Hz with a XeF gas mixture (351 nm). The telescope is a .75m horizontally mounted Dall-Kirkham system which is bore sited with a .8m x 1.1m elliptical flat which has a full 180 degree scan capability - horizon to horizon within a plane perpendicular to the long axis of the trailer. The telescope and scan mirror assembly are mounted on a 3.65m x .9m optical table which deploys out the rear of the trailer through the use of a motor driven slide rail system. The Raman returns from water vapor (403 nm), nitrogen (383 nm) and oxygen (372 nm) are measured in addition to the direct Rayleigh/Mie backscatter (351). The signal from each of these is split at about a 5/95 ratio between two photomultiplier detectors. The 5 percent detector is used for

  13. Water vapor in protoplanetary disks

    NASA Astrophysics Data System (ADS)

    Banzatti, Andrea

    2013-03-01

    This thesis is devoted to a study of the conditions and evolution of the planet formation region in young circumstellar disks, by means of spectroscopic observations of molecular gas emission. The main focus of this work is the infrared spectrum of water (H2O), which provides thousands of emission lines tracing the warm and dense gas inward of the water snow line in disks. The analysis includes also emission from some organic molecules that trace the carbon chemistry, C2H2, HCN, and CO2, as well as emission from OH that is connected to the formation and destruction of the water molecule. Two are the main directions explored in this work, for which we used spectra from the Spitzer Space Telescope (IRS) and the Very Large Telescope (VISIR and X-shooter). The first is to investigate how variable accretion phenomena occurring during the T Tauri phase affect the molecular environments in the planet formation region of disks. By monitoring T Tauri stars in different phases of accretion, we found that outbursts can remarkably affect their mid-infrared molecular emission. We propose a scenario where accretion flares trigger a recession of the water snow line, increasing water emission from the disk, when the accretion luminosity keeps higher over long enough timescales for the thermal structure of the disk to change (at least a few weeks, as observed in the strongly variable EX Lupi). In addition, enhanced UV radiation is found to produce OH from photodissociation of water in the disk. Organic molecules instead disappear during a strong outburst, and we are currently investigating the long-term evolution of these effects. A second direction was taken to tackle another fundamental problem: the origin of water vapor in inner disks. Some models predict that water is produced by evaporation of icy solids migrating inward of the snow line. One way to probe this scenario is by measuring the abundance of water vapor in the inner disk, and compare it to the oxygen abundance

  14. Vapor Compression Distillation Flight Experiment

    NASA Technical Reports Server (NTRS)

    Hutchens, Cindy F.

    2002-01-01

    One of the major requirements associated with operating the International Space Station is the transportation -- space shuttle and Russian Progress spacecraft launches - necessary to re-supply station crews with food and water. The Vapor Compression Distillation (VCD) Flight Experiment, managed by NASA's Marshall Space Flight Center in Huntsville, Ala., is a full-scale demonstration of technology being developed to recycle crewmember urine and wastewater aboard the International Space Station and thereby reduce the amount of water that must be re-supplied. Based on results of the VCD Flight Experiment, an operational urine processor will be installed in Node 3 of the space station in 2005.

  15. Chemical vapor deposition of sialon

    DOEpatents

    Landingham, Richard L.; Casey, Alton W.

    1982-01-01

    A laminated composite and a method for forming the composite by chemical vapor deposition. The composite includes a layer of sialon and a material to which the layer is bonded. The method includes the steps of exposing a surface of the material to an ammonia containing atmosphere; heating the surface to at least about 1200.degree. C.; and impinging a gas containing in a flowing atmosphere of air N.sub.2, SiCl.sub.4, and AlCl.sub.3 on the surface.

  16. Microwave assisted chemical vapor infiltration

    SciTech Connect

    Devlin, D.J.; Currier, R.P.; Barbero, R.S.; Espinoza, B.F.; Elliott, N.

    1991-12-31

    A microwave assisted process for production of continuous fiber reinforced ceramic matrix composites is described. A simple apparatus combining a chemical vapor infiltration reactor with a conventional 700 W multimode oven is described. Microwave induced inverted thermal gradients are exploited with the ultimate goal of reducing processing times on complex shapes. Thermal gradients in stacks of SiC (Nicalon) cloths have been measured using optical thermometry. Initial results on the ``inside out`` deposition of SiC via decomposition of methyltrichlorosilane in hydrogen are presented. Several key processing issues are identified and discussed. 5 refs.

  17. Photoluminescence studies on the complexation of Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitrate medium

    NASA Astrophysics Data System (ADS)

    Pathak, P. N.; Mohapatra, M.; Godbole, S. V.

    2013-11-01

    UREX process has been proposed for selective extraction of U(VI) and Tc(VII) from nitric acid medium (∼1 M HNO3) using tri-n-butyl phosphate (TBP) as extractant and retaining Pu, Np and fission products in the aqueous phase. The feasibility of the use of luminescence spectroscopy as a technique to understand the complexation of trivalent f-elements cations viz. Eu(III) and Tb(III) with acetohydroxamic acid (AHA) in nitric acid medium has been examined. The luminescence lifetimes for the 1 × 10-3 M Eu(III) and AHA complex system decreased with increased AHA concentration from 116 ± 0.2 μs (no AHA) to 1.6 ± 0.1 μs (0.1 M AHA) which was attributed to dynamic quenching. The corrected fluorescence intensities were used to calculate the stability constant (log K) for the formation of 1:1 Eu3+-AHA complex as 1.42 ± 0.64 under the conditions of this study. By contrast, the Tb(III)-AHA system at pH 3 (HNO3) did not show any significant variation in the life times of the excited state (364 ± 9 μs) suggesting the absence of dynamic quenching. The spectral changes in Tb(III)-AHA system showed the formation of 1:1 complex (log K: 1.72 ± 0.21). These studies suggest that the extent of AHA complexation with the rare earth elements will be insignificant as compared to tetravalent metal ions Pu(IV) and Np(IV) under UREX process conditions.

  18. Desorption of 137Cs from Brachythecium mildeanum moss using acid solutions with pH 4.60-6.50

    NASA Astrophysics Data System (ADS)

    Čučulović, Ana; Veselinović, Dragan

    2015-12-01

    The desorption of 137Cs from the moss Brachythecium mildeanum (Schimp.) was performed using the following solutions: H2SO4 ( I), HNO3 ( II), H2SO4 + HNO3 ( III) with pH values of 4.60, 5.15, and 5.75, respectively, as well as distilled water (D) with pH 6.50. After five successive desorptions, each lasting 24 h, 20.5-37.6% 137Cs was desorbed from the moss using these solutions, while 30.7% of the starting content was desorbed using distilled water. The first desorption removed the highest percent of the original content of 137Cs in the moss (11.3-18.4%). This was determined by measuring 137Cs activity. If the current results are compared with those obtained earlier it may be concluded that 137Cs desorption from mosses is not species-dependent. The obtained results indicate the necessity of investigating the influence of acid rain, or rather, of H+ ions, on desorption of other ions from biological systems, i.e., the role of H+ ions in spreading other polluting compounds and thus producing secondary environmental pollution. From the results of this study it follows that acid rain will lead, through H+ ion action, to a similar increasing pollution of fallout waters with other ionic compounds which may not be present in the water before the contact with the plants and thus enable the pollution spreading. In the investigated system, the replacement of H+ ions from acid rains by more dangerous radioactive ions occured, increasing the concentration of the radioactive ions in the water, which demonstrates that the same process takes place in fallout water.

  19. Control of flow through a vapor generator

    DOEpatents

    Radcliff, Thomas D.

    2005-11-08

    In a Rankine cycle system wherein a vapor generator receives heat from exhaust gases, provision is made to avoid overheating of the refrigerant during ORC system shut down while at the same time preventing condensation of those gases within the vapor generator when its temperature drops below a threshold temperature by diverting the flow of hot gases to ambient and to thereby draw ambient air through the vapor generator in the process. In one embodiment, a bistable ejector is adjustable between one position, in which the hot gases flow through the vapor generator, to another position wherein the gases are diverted away from the vapor generator. Another embodiment provides for a fixed valve ejector with a bias towards discharging to ambient, but with a fan on the downstream side of said vapor generator for overcoming this bias.

  20. Cluster model of aluminum dense vapor plasma

    NASA Astrophysics Data System (ADS)

    Khomkin, A. L.; Shumikhin, A. S.

    2009-08-01

    The chemical model of aluminum vapor plasma, that take into account the formation of neutral and charged clusters, is suggested. Caloric and thermal equations of state and composition of plasma were received using the available information about properties of metal clusters. It is shown, that aluminum vapors are clusterized with decrease of temperature and with increase of density. Pressure dependence on internal energy is calculated and comparison with experimental data is made. The important role of aluminum clusters, especially in an initial phase of the metals vapor heating, is demonstrated. It is shown, that the region of plasma clusterization in gaseous phase agree with known literature data for binodal of vapor-liquid transition from gaseous region. Suggested cluster model may be used to forecast the location of metal vapors binodal. The conductivity of aluminum vapor plasma was calculated. The satisfactory agreement with available experimental data is received.

  1. Profiling atmospheric water vapor by microwave radiometry

    NASA Technical Reports Server (NTRS)

    Wang, J. R.; Wilheit, T. T.; Szejwach, G.; Gesell, L. H.; Nieman, R. A.; Niver, D. S.; Krupp, B. M.; Gagliano, J. A.; King, J. L.

    1983-01-01

    High-altitude microwave radiometric observations at frequencies near 92 and 183.3 GHz were used to study the potential of retrieving atmospheric water vapor profiles over both land and water. An algorithm based on an extended kalman-Bucy filter was implemented and applied for the water vapor retrieval. The results show great promise in atmospheric water vapor profiling by microwave radiometry heretofore not attainable at lower frequencies.

  2. Droplet Vaporization in a Supercritical Microgravity Environment

    NASA Technical Reports Server (NTRS)

    Curtis, E. W.; Farrell, P. V.

    1987-01-01

    A model is presented which describes single liquid droplet vaporization at nearly critical liquid pressures and temperatures. A modified Redlich-Kwong equation of state is used to evaluate the fugacities and liquid and vapor mole fractions at the interface under the assumption of interface equilibrium. Results obtained for different droplet sizes and conditions indicate significant differences in behavior in comparison with low-pressure quasi-steady droplet vaporization.

  3. Droplet vaporization in a supercritical microgravity environment

    NASA Astrophysics Data System (ADS)

    Curtis, E. W.; Farrell, P. V.

    1987-10-01

    A model is presented which describes single liquid droplet vaporization at nearly critical liquid pressures and temperatures. A modified Redlich-Kwong equation of state is used to evaluate the fugacities and liquid and vapor mole fractions at the interface under the assumption of interface equilibrium. Results obtained for different droplet sizes and conditions indicate significant differences in behavior in comparison with low-pressure quasi-steady droplet vaporization.

  4. Vapor Pressure Data Analysis and Statistics

    DTIC Science & Technology

    2016-12-01

    several assumptions that are not exact. These are, primarily, that heat of vaporization (the slope of the vapor pressure curve) does not vary with...account the variation in heat of vaporization with temperature, and accurately describes data over broad experimental ranges, thereby enabling...units; however, the fit determined using one unit system will only correspond to that using the same data in another unit system if unrounded values

  5. Gravity sensitivity of a resistojet water vaporizer

    NASA Technical Reports Server (NTRS)

    Morren, W. Earl

    1993-01-01

    A laboratory model of a water vaporizer for resistojet applications was designed, fabricated, and steady and transient characteristics were measured. Vaporizer operation was not impacted by rotation about a horizontal axis normal to its own. The vaporizer was operated under low and high accelerations aboard a jet aircraft for periods up to 25 s at flow rates ranging from 159(10)(exp -6) to 230(10)(exp -6) kg/s. Slight changes in inlet and outlet pressures and some heat exchanger temperatures were observed during the low-gravity tests. However, the results of these tests indicated probable compatibility of the vaporizer design tested with a low-gravity environment.

  6. X-ray-induced water vaporization

    SciTech Connect

    Weon, B. M.; Lee, J. S.; Je, J. H.; Fezzaa, K.

    2011-09-15

    We present quantitative evidence for x-ray-induced water vaporization: water is vaporized at a rate of 5.5 pL/s with the 1-A-wavelength x-ray irradiation of {approx}0.1 photons per A{sup 2}; moreover, water vapor is reversibly condensed during pauses in irradiation. This result fundamentally suggests that photoionization induces vaporization. This phenomenon is attributed to surface-tension reduction by ionization and would be universally important in radiological and electrohydrodynamic situations.

  7. Chemistry of vaporization of refractory materials

    NASA Technical Reports Server (NTRS)

    Gilles, P. W.

    1975-01-01

    A discussion is given of the principles of physical chemistry important in vaporization studies, notably the concepts of equilibrium, phase behavior, thermodynamics, solid solution, and kinetics. The important factors influencing equilibrium vaporization phenomena are discussed and illustrated. A proper course of a vaporization study consisting of 9 stages is proposed. The important experimental techniques of Knudsen effusion, Langmuir vaporization and mass spectrometry are discussed. The principles, the factors, the course of a study and the experimental techniques and procedures are illustrated by recent work on the Ti-O system.

  8. Heterogeneous Vapor Condensation in Boundary Layers

    SciTech Connect

    Bonilla, L. L.; Carpio, A.; Neu, J. C.

    2008-09-01

    We consider heterogeneous condensation of vapors mixed with a carrier gas in stagnation point boundary layer flow near a cold wall in the presence of solid particles much larger than the mean free path of vapor particles. The supersaturated vapor condenses on the particles by diffusion, particles and droplets are thermophoretically attracted to the wall. We sketch three asymptotic theories of the condensation process, calculate the flow-induced shift in the dew point interface, vapor density profile and deposition rates at the wall, and compare them to direct numerical simulation.

  9. A vapor generator for transonic flow visualization

    NASA Technical Reports Server (NTRS)

    Bruce, Robert A.; Hess, Robert W.; Rivera, Jose A., Jr.

    1989-01-01

    A vapor generator was developed for use in the NASA Langley Transonic Dynamics Tunnel (TDT). Propylene glycol was used as the vapor material. The vapor generator system was evaluated in a laboratory setting and then used in the TDT as part of a laser light sheet flow visualization system. The vapor generator provided satisfactory seeding of the air flow with visible condensate particles, smoke, for tests ranging from low subsonic through transonic speeds for tunnel total pressures from atmospheric pressure down to less than 0.1 atmospheric pressure.

  10. Mars water vapor, near-surface

    NASA Technical Reports Server (NTRS)

    Ryan, J. A.; Sharman, R. D.; Lucich, R. D.

    1982-01-01

    In a previous paper we concluded that the temperature sensors aboard the Viking landers (VL-1 and VL-2) were detecting the water vapor frost point. Analysis of one Mars year of data at both lander sites substantiates this conclusion. At VL-1 it is found that the water vapor mixing ratio is constant with height through the bulk of the atmosphere, most of the time. Exceptions are during the onset phases of the two major dust storms when temporary enhancement of near-surface vapor occurs (the same phenomenon is observed at VL-2), and some depletion of near-surface vapor during the decay phase of the first storm, possibly the second storm as well. The former suggests near-surface, northward transport of water vapor with the storms. The latter suggests adsorption of vapor on dust particles followed by surface deposition. At VL-2, severe near-surface depletion of water vapor occurs during northern autumn and winter. The residual vapor is in equilibrium with the surface condensate observed at the site during this period, indicating that the source region for the condensate must be aloft with downward transport by dust fall-out. Since the near-surface water vapor mixing ratio and concentration at VL-1 generally parallels the column abundance over VL-1 obtained by the orbiters, this suggests that VL-1 can be used to give a measure of column abundance for as long as the temperature sensors remain operational.

  11. Water vapor, whence comest thou.

    NASA Technical Reports Server (NTRS)

    Freeman, J. W., Jr.; Hills, H. K.; Vondrak, R. R.

    1972-01-01

    During a 14-hour period on Mar. 7, 1971, the Apollo 14 ALSEP suprathermal ion detector experiment (SIDE) observed an intense, prolonged series of bursts of 48.6-eV ions at the lunar surface. The SIDE mass analyzer showed the mass per unit charge of these ions to be characteristic of water vapor if singly ionized. The event was also observed by the SIDE total ion detectors (TIDs) at the Apollo 14 site and at Apollo 12 (located 183 km to the west). The TID data from SIDE 14 indicate that the energy spectrum was narrower than the 20-eV interval between energy channels. Ion spectra due to the LM exhaust gases are shown to be readily identified by the SIDE and are distinctly different in character from the spectra obtained on March 7. Detailed consideration of other possible sources of water, including the Apollo 14 CSM, leads to the conclusion that the water vapor did not come from a man-made source. Also, it is estimated that the event may have involved a quantity of water much greater than that which has been artificially introduced into the lunar environment. Consequently, it appears to be of lunar origin.

  12. The effect of sulfur on vapor liquid fractionation of metals in hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Pokrovski, Gleb S.; Borisova, Anastassia Yu.; Harrichoury, Jean-Claude

    2008-02-01

    Despite the growing evidence that the vapor phase, formed through magma degassing and ore fluid boiling, can selectively concentrate and transport metals, the effects of major volatile components like sulfur, chlorine or carbon dioxide on the metal vapor-liquid fractionation and vapor-phase transport under magmatic-hydrothermal conditions remain poorly known. We performed systematic experiments to investigate the effect of sulfur ligands on metal vapor-liquid partitioning in model H 2O-S-NaCl-KCl-NaOH systems at temperatures from 350 to 500 °C. Results show that at acidic-to-neutral conditions, vapor-liquid equilibrium distribution coefficients, Km = mvapor / mliquid, where m is the mass concentration of the metal in corresponding phase, of metalloids (As, Sb) and base metals (Zn, Fe, Pb, Ag) are in the range 0.1-1.0 and 0.001-0.1, respectively, and are not significantly affected by the presence of geologically common sulfur concentrations, up to 1-3 wt.% S. In contrast, the partitioning of Cu, Au, and Pt into the vapor increases by a factor of 100 in comparison to the S-free water-salt system, yielding Km values of 0.5-1.0, 1-10, and 10-20, respectively, due to formation of volatile neutral complexes with H 2S and, possibly, SO 2. In neutral-to-basic systems, Zn, Pb, Fe and Ag show 10-100-fold increase of their partition coefficients, whereas Cu, Au and Pt exhibit Km values of up to several orders of magnitude lower, compared to acidic conditions at similar temperature, pressure and sulfur contents. These vapor-liquid distribution patterns result from combined effects of i) formation of volatile species with reduced sulfur ligands in the vapor phase, ii) changes in the metal speciation in the coexisting liquid phase as a function of pH, and iii) solute-solvent interactions in both phases. Our data explain the vapor-liquid fractionation trends for many metals as inferred in coexisting brine and vapor inclusions from magmatic-hydrothermal deposits, and provide a

  13. 33 CFR 154.828 - Vapor recovery and vapor destruction units.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... line; and (3) Alarm and shut down when a flame is detected on the flame arrester or detonation arrester. (d) When a vapor destruction unit shuts down or has a flame-out condition the vapor destruction...

  14. Parallel-plate wet denuder coupled ion chromatograph for near-real-time detection of trace acidic gases in clean room air.

    PubMed

    Takeuchi, Masaki; Tsunoda, Hiromichi; Tanaka, Hideji; Shiramizu, Yoshimi

    2011-01-01

    This paper describes the performance of our automated acidic (CH(3)COOH, HCOOH, HCl, HNO(2), SO(2), and HNO(3)) gases monitor utilizing a parallel-plate wet denuder (PPWD). The PPWD quantitatively collects gaseous contaminants at a high sample flow rate (∼8 dm(3) min(-1)) compared to the conventional methods used in a clean room. Rapid response to any variability in the sample concentration enables near-real-time monitoring. In the developed monitor, the analyte collected with the PPWD is pumped into one of two preconcentration columns for 15 min, and determined by means of ion chromatography. While one preconcentration column is used for chromatographic separation, the other is used for loading the sample solution. The system allows continuous monitoring of the common acidic gases in an advanced semiconductor manufacturing clean room.

  15. Acidic and alkaline pretreatments of activated carbon and their effects on the performance of air-cathodes in microbial fuel cells.

    PubMed

    Wang, Xin; Gao, Ningshengjie; Zhou, Qixing; Dong, Heng; Yu, Hongbing; Feng, Yujie

    2013-09-01

    Activated carbon (AC) is a high performing and cost effective catalyst for oxygen reduction reactions (ORRs) of air-cathodes in microbial fuel cells (MFCs). Acidic (HNO3) and alkaline (KOH) pretreatments on AC at low temperature (85°C) are conducted to enhance the performance of MFCs. The alkaline pretreatment increased the power density by 16% from 804±70 to 957±31 mW m(-2), possibly due to the decrease of ohmic resistance (from 20.58 to 19.20 Ω) and the increase of ORR activities provided by the adsorbed hydroxide ion and extra micropore area/volume after alkaline pretreatment. However, acidic pretreatment decreased the power output to 537±36 mW m(-2), which can be mainly attributed to the corrosion by adsorbed proton at the interface of AC powder and stainless steel mesh and the decreased pore area.

  16. Soluble species in the Arctic summer troposphere: Acidic gases, aerosols, and precipitation

    NASA Astrophysics Data System (ADS)

    Talbot, R. W.; Vijgen, A. S.; Harriss, R. C.

    1992-10-01

    We report here the distribution of selected acidic gases and aerosol species in the North American Arctic and sub-Arctic summer troposphere. The summertime troposphere is an acidic environment, with HCOOH and CH3COOH the principal acidic gases and acidic sulfate aerosols dominating the particulate phase. Our data show that the acidic gas and aerosol composition is uniform on a large spatial scale. There appears to be a surface source of NH4+ over the Arctic Ocean pack ice which may reflect release of NH3 from decay of dead marine organisms on the ice surface near ice leads, release from rotting sea ice, or an upward flux from surface ocean waters in open ice leads. This NH3 appears to partially neutralize aerosol acidity in the boundary layer. Over sub-Arctic tundra in southwestern Alaska inputs of marine biogenic sulfur from the nearby Bering Sea appear to be an important source of boundary layer aerosol SO42-. While there were only minor effects on aerosol chemistry over the tundra from sea salt, the rainwater chemistry showed influence from marine aerosols which were apparently incorporated into air masses during frontal passages moving inland from the Bering Sea. The rainwater acidity over the tundra (pH 4.69) is typical of remote regions. The principal acidity components are H2SO4 and carboxylic acids, especially HCOOH. The carboxylic acids appear to have a strong continental biogenic source, but hydrocarbons of marine origin and emissions from forest fires may also be important. The wet deposition fluxes of NO3--N and SO42--S over sub-Arctic tundra during July-August 1988 were 2.1 and 2.4 mmol m-2 yr-1. Wet deposition of NO3- was nearly 3 times higher than the average NOy deposition flux, which is believed to represent primarily dry deposition of HNO3 (Bakwin et al., this issue). Our measurements indicate that the mid-troposphere in the Arctic is generally contaminated with low levels of anthropogenic pollutants even in summer when direct atmospheric coupling

  17. Microstructure and Corrosion Behavior of Hf-40 Wt Pct Ti Alloy in Nitric Acid Medium for Reprocessing Applications

    NASA Astrophysics Data System (ADS)

    Jayaraj, J.; Ravi, K. R.; Mallika, C.; Kamachi Mudali, U.

    2016-09-01

    The Hf-40 wt pct Ti (Hf-Ti) alloy was developed for neutron poison application in the spent nuclear fuel reprocessing plant. The furnace-cooled Hf-Ti sample exhibited the microstructure comprising equiaxed-α, lamellar-α, and feathery-α. The water-quenched Hf-Ti sample confirmed the presence of lath and internally twinned martensite. In comparison to the furnace-cooled sample, low corrosion current density and passivation current density values obtained for the water-quenched Hf-Ti in 6 M HNO3 at 298 K (25 °C) indicated better passivation ability. The martensitic structure exhibited high hardness (660 HV) and negligible corrosion rate in 6 M nitric acid at 298 K (25 °C). X-ray photoelectron spectroscopic (XPS) analysis confirmed that passivation behavior of this alloy was due to the protective passive film composed of TiO2 and HfO2.

  18. Ab initio study of the molecular structure and vibrational spectrum of nitric acid and its protonated forms

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Rice, Julia E.

    1992-01-01

    The equilibrium structures, harmonic vibrational frequencies, IR intensities, and relative energetics of HNO3 and its protonated form H2NO3+ were investigated using double-zeta plus polarization and triple-zeta plus polarization basis sets in conjunction with high-level ab initio methods. The latter include second-order Moller-Plesset perturbation theory, the single and double excitation coupled cluster (CCSD) methods, a perturbational estimate of the effects of connected triple excitations (CCSD(T)), and the self-consistent field. To determine accurate energy differences CCSD(T) energies were computed using large atomic natural orbital basis sets. Four different isomers of H2NO3+ were considered. The lowest energy form of protonated nitric acid was found to correspond to a complex between H2O and NO2+, which is consistent with earlier theoretical and experimental studies.

  19. Aerosol silica as a possible candidate for the heterogeneous formation of nitric acid hydrates in the stratosphere

    NASA Astrophysics Data System (ADS)

    Bogdan, A.; Kulmala, M.

    The liquid-solid phase transitions in nanometersize HNO3/H2O solution droplets obtained on fumed silica (a counterpart of aerosol silica) have been studied with differential scanning calorimetry (DSC). “Soft” transitions, reduction in the freezing and melting temperatures, Tf and Tm, and enthalpies, ΔHf and ΔHm, are interpreted to be caused by very small size of droplets. The observed difference between ΔHf and ΔHm can serve as an evidence of temperature dependence of the enthalpy of fusion for hydrates. Freezing of droplets with stoichiometry close to nitric acid trihydrate (NAT) at temperature 4 K warmer than the ice frost point indicates that, in the stratosphere, silica particles can serve as nuclei for heterogeneous freezing of NAT.

  20. Near real time vapor detection and enhancement using aerosol adsorption

    DOEpatents

    Novick, Vincent J.; Johnson, Stanley A.

    1999-01-01

    A vapor sample detection method where the vapor sample contains vapor and ambient air and surrounding natural background particles. The vapor sample detection method includes the steps of generating a supply of aerosol that have a particular effective median particle size, mixing the aerosol with the vapor sample forming aerosol and adsorbed vapor suspended in an air stream, impacting the suspended aerosol and adsorbed vapor upon a reflecting element, alternatively directing infrared light to the impacted aerosol and adsorbed vapor, detecting and analyzing the alternatively directed infrared light in essentially real time using a spectrometer and a microcomputer and identifying the vapor sample.