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At least 217 records · Page 12

Low-pressure study of the HO2 + HO2 reaction at 298 K

The rate constant for the reaction HO2 + HO2 yields H2O2 + O2 was measured at 298 K and 1 torr total pressure of helium by using the discharge flow technique. A quadrupole mass spectrometer was used to detect HO2 in conjunction with in situ long-path ultraviolet absorption which was used for calibration. A value of 1.5 + or - 0.4 x 10 to the -12th per molecule/s was obtained for k1 where the rate constant is defined by the relation -d(HO2)/dt = 2K1(HO2)HO2.

Sander, S. P.↗

Detection of atomic oxygen and further line assignments in the far-infrared stratospheric spectrum

Recent progress in high-resolution measurement of sub-millimeter and far-infrared emission in the stratosphere is reviewed. Attention is given to the results of recent balloon measurements of the minor stratospheric constituents in the spectral range 40-190 per cm. Emission spectra are presented for HCl; HF; and OH. Emission spectra were also obtained for atomic oxygen; hydrobromic acid; and hydroperoxyl radical. The possibility of detecting HO2 and H2O2 in the far-infrared is also briefly discussed.

Carli, B.↗

A balloon-borne microwave limb sounder for stratospheric measurements

The balloon-borne microwave limb sounder (BMLS) measures atmospheric thermal emission from millimeter wavelength spectral lines to determine vertical profiles of stratospheric species. The instrument flown to date operates at 205 GHz to measure ClO, O3, and H2O2. A 63 GHz radiometer will be added to test the technique for determining tangent point pressure from the MLS experiment on the upper atmosphere research satellite (UARS). Many additional species could also be measured by the BMLS. A radiometer at 270 GHz would provide measurements of HO2, NO2, HNO3, N2O, O-16O-18O-16, and HCN. With this addition, the BMLS can test the current theory of O3 photochemical balance in the upper stratosphere.

Waters, J. W.↗

Microwave limb sounder for stratospheric measurements

The balloon-borne Microwave Limb Sounder (BMLS) measures atmospheric thermal emission from millimeter wavelength spectral lines to determine vertical profiles of stratospheric species. The instrument flown to data operates at 205 BHz to measure ClO, O3, and H2O2. A 63 GHz radiometer is added to test the technique for determining tangent point pressure from the MLS experiment on the Upper Atmosphere Research Satellite (UARS). Many additional species is also measured by the BLMS. A radiometer at 270 GHz would provide measurements of HO2, NO2, HNO3, N2O, 16O18O16O, and HCN. With this addition the BMLS can test the current theory of O3 heavy ozone photochemical balance in the upper stratosphere.

Waters, J. W.↗

Interstellar grain mantles

Interstellar molecular grain mantles are an important component of the interstellar dust inside dense molecular clouds as evidenced by the detection of absorption bands at 2.97, 3.08, 4.61, 6.0 and 6.8 microns. Mantles may also be the precursors of more complex grain mantles in the diffuse interstellar medium. The molecular composition of these icy grain mantles were calculated employing gas phase as well as grain surface reactions. The calculated mixtures consist mainly of the molecules H2O, H2CO, N2, CO, O2, H2O2, NH2, and their deuterated counterparts in varying ratios. The exact compositions depend strongly on the physical conditions in the gas phase. The absorption spectra of H2O with other molecules was studied in the laboratory. Optical constants were determined for a few selected mixtures. Extinction and polarization cross sections across the 3 micron ice band were calculated. A comparison with the observations towards BN shows that the low frequency wing observed on this feature is due to absorption by a mixture of H2O and other molecules rather than scattering by large, pure H2O ice grains.

Bregman, J.↗

Hydrogen species

Measurements of the members of the HO(x) family (OH, HO2, and H2O2) and their major source gases, H2O, and CH4 are discussed. Emphasis is placed on measurements which were made since the 1982 World Meteorologic Organization (WMO) report. Measurement techniques, available data, an assessment of data reliability, and a comparison of the data with theoretical distributions of stratospheric HO(x) species predicted from one and two dimensional photochemical models are discussed.

Schiff, H. I.↗

Oxidant abundances in rainwater and the evolution of atmospheric oxygen

H2O2 is probably the dominant oxidant in rainwater at O2 levels lower than 0.01-0.001 present atmospheric levels (PAL), and the magnitude of its dissolved flux is sensitive to the concentration of the trace gases NO, CO, and CH4 in the atmosphere, as well as to the partial pressure of atmospheric CO2. The earlier interpretation of the paleosol data in terms of the ratio of p-O2/p-CO2 in the atmosphere must be modified by taking into account the effects of photochemically produced oxidants and reactants at p-O2 of les than 0.01 PAL.

Kasting, J. F.↗

Direct picosecond time resolution of unimolecular reactions initiated by local mode excitation

Attention is given to the first results of direct, picosec measurements of the Delta-nu(OH) 5 local mode transition of H2O2. These time-resolved studies yield a direct measure of the unimolecular dissociation rate, and furnish a lower limit for the rate of energy redistribution from the OH stretch to the O-O reaction coordinate. The data thus determined may be used to ascertain the domain of validity for statistical unimolecular reaction rate theories.

Scherer, N. F.↗

Enhancing effects of gamma interferon on phagocytic cell association with and killing of Trypanosoma cruzi

Results are reported from a study of the influence gamma interferon (GIFN) and interleukin 2 (IL2) have on the capability of P388D1 cells and mouse resident peritoneal macrophages (MPM) to attach to the blood-resident parasites Trypanosoma cruzi and kill them. Cultures of trypomastigote forms of the Tulahuen strain of T. cruzi grown in bovine serum were introduced into peritoneal cells of mice, along with P388D1 cells incubated with GIFN, IL2 and both. Control cells were also maintained. Statistical analysis were then performed on data on counts of the number of dead T. Cruzi cells. The GIFN enhanced the interaction of MPM and P388D1 cells with the surface of T. Cruzi, provided the interaction was given over 12 hr to take place. A depression of the cytotoxicity of P388D1 cells was attributed to mediation by H2O2, an effect partially offset by incubation with the lymphokine GIFN.

Wirth, J. J.↗

Future directions for H sub x O sub y detection, executive summary

New methods for the measurement of OH radicals were assessed as were currently available and possible future methods for the other H sub x O sub y species, HO2 and H2O2. The workshop participants were invited from different groups: modelers of atmospheric photochemistry, experimentalists measuring H sub x O y species with laser and nonlaser methods, and chemists and physicists familiar with such experiments but not involved in atmospheric monitoring. There were three major conclusions from the workshop concerning the OH radical. First, it was felt that local measurements made by laser techniques would be ready within 2 or 3 years to furnish reliable measurements at the level of 1,000,000 cu. cm. Second, measurements at this level of sensitivity and with attainable levels of precision could indeed be used to make useful and interesting tests of the fast photochemistry of the troposphere. It is important, however, that the measurements be carefully designed, with respect to spatial and temporal averaging, if there is to be a meaningful comparison between results from two experimental methods or a measurement and a model. Third, nonlocal measurements using released reactants and tracers would also be very useful. These could be made on a regional or global basis, although they still require experimental design including choice of compounds.

Source record↗

Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.

Cooper, David E.↗

Hydrogen oxidation mechanism with applications to (1) the chaperon efficiency of carbon dioxide and (2) vitiated air testing

Ignition delay times for the hydrogen/oxygen/carbon dioxide/argon system were obtained behind reflected shock waves. A detailed kinetic mechanism modeled the experimental hydrogen/oxygen data, Skinner and Ringrose's high-pressure data, and Slack and Grillo's hydrogen/air data. A carbon dioxide chaperon efficiency of 7.0 +/- 0.2 was determined. The reaction pathway H2O yields H2O2 yields OH yields H was required to model the high-pressure data. It is suggested that some of the lowest temperature data points (1.0 and 0.5 atm) for Slack and Grillo's hydrogen/air experiments are in error. It was found that the technique of simplifying a detailed kinetic mechanism for a limited range of experimental data may render the model useless for other test conditions.

Brabbs, Theodore A.↗

Atlas of Absorption Lines from 0 to 17900 Cm (sup)-1

Plots of logarithm (base 10) of absorption line strength versus wavenumber from 0 to 17900/cm(sup)-1 are shown for the 28 atmospheric gases (H2O, CO2, O3, N2O, CO, CH4, O2, NO, SO2, NO2, NH3, HNO3, OH, HF, HCl, HBr, HI, ClO, OCS, H2CO, HOCl, N2, HCN, CH3Cl, H2O2, C2H2, C2H6, PH3), which appear in the 1986 Air Force Geophysics Laboratory high-resolution transmission molecular absorption data base (HITRAN) compilation, and for O(P-3), O-18 isotopic ozone, and HO2 from the 1984 JPL compilation in the 0- to 200/cm(sup)-1 region, and infrared solar CO lines at 4500 K. Also shown are plots of logarithm (base 10) of approximate infrared absorption cross sections of 11 heavy molecules versus wavenumber. The cross-section data cover 700 to 1800/cm(sup)-1 and are included as a separate data file in the 1986 HITRAN database.

Park, J. H.↗

Advanced fuel cell concepts for future NASA missions

Studies of primary fuel cells for advanced all electric shuttle type vehicles show an all fuel cell power system with peak power capability of 100's of kW to be potentially lighter and have lower life cycle costs than a hybrid system using advanced H2O2 APU's for peak power and fuel cells for low power on orbit. Fuel cell specific weights of 1 to 3 lb/kW, a factor of 10 improvement over the orbiter power plant, are projected for the early 1990's. For satellite applications, a study to identify high performance regenerative hydrogen oxygen fuel cell concepts for geosynchronous orbit was completed. Emphasis was placed on concepts with the potential for high energy density (Wh/lb) and passive means for water and heat management to maximize system reliability. Both alkaline electrolyte and polymer membrane fuel cells were considered.

Stedman, J. K.↗

The GEISA spectroscopic line parameters data bank in 1984

The 1984 update of the GEISA data bank, containing spectroscopic information on 323,521 lines corresponding to 36 molecules and 79 isotopic species in the spectal range 3 x 10 to the -6th/cm to 17,879/cm, is discussed. The bank compiles parameters describing the radiation absorption or emission properties of gases involved in the atmospheres of the earth and planets. Values of a new exponent which summarized the variation of the collision halfwidth with temperature are given for 10 molecules. Six new molecules, HOCl, N2, CH3Cl, H2O2, H2S, and HCOOH, are included in this edition.

Husson, N.↗

Aqueous sodium chloride induced intergranular corrosion of Al-Li-Cu alloys

Two methods have been explored to assess the susceptibility of Al-Li-Cu alloys to intergranular corrosion in aqueous sodium chloride solution. They are: (1) constant extension rate testing with and without alternate-immersion preexposure and (2) metallographic examination after exposure to a NaCl-H2O2 corrosive solution per Mil-H-6088F. Intergranular corrosion was found to occur in both powder and ingot metallurgy alloys of similar composition, using both methods. Underaging rendered the alloys most susceptible. The results correlate to stress-corrosion data generated in conventional time-to-failure and crack growth-rate tests. Alternate-immersion preexposure may be a reliable means to assess stress corrosion susceptibility of Al-Li-Cu alloys.

Pizzo, P. P.↗

The carbon dioxide chaperon efficiency for the reaction H + O2 + M yields HO2 + M from ignition delay times behind reflected shock waves

Ignition delay times for stoichiometric hydrogen-oxygen in argon with and without carbon dioxide were measured behind reflected shock waves. A 20-reaction kinetic mechanism models the measured hydrogen-oxygen delay times over the temperature range 950 to 1300 K. The chaperon efficiency for carbon dioxide determined for the hydrogen-oxygen carbon dioxide mixture was 7.0. This value is in agreement with literature values but much less than a recent value obtained from flow tube experiments. Delay times measured behind a reflected shock wave were about 20% longer than those measured behind incident shock waves. The kinetic mechanism successfully modeled the high-pressure data of Skinner and the hydrogen-air data of Stack. It is suggested that the lowest temperature points for the hydrogen-air data of Slack are unreliable and that the 0.27-atm data may illustrate a case where vibrational relaxation of nitrogen is important. The reaction pathway HO2 yields H2O2 yields OH yields H was required to model the high-pressure data of Skinner. The successful modeling of the stoichiometric hydrogen-air data demonstrates the appropriateness of deriving kinetic models from data for gas mixtures highly diluted with argon. The technique of reducing a detailed kinetic mechanism to only the important reactions for a limited range of experimental data may render the mechanism useless for other test conditions.

Brabbs, Theodore A.↗

Copper peroxide

A number of oxidizing agents, including chlorine, bromine, ozone and other peroxides, were allowed to act on copper solutions with the intention of forming copper peroxide. The only successful agent appears to be hydrogen peroxide. It must be used in a neutral 50 to 30 percent solution at a temperature near zero. Other methods described in the literature apparently do not work. The excess of hydrogen must be quickly sucked out of the brown precipitate, which it is best to wash with alcohol and ether. The product, crystalline under a microscope, can be analyzed only approximately. It approaches the formula CuO2H2O. In alkaline solution it appears to act catalytically in causing the decomposition of other peroxides, so that Na2O2 cannot be used to prepare it. On the addition of acids the H2O2 is regenerated. The dry substance decomposes much more slowly than the moist but is not very stable.

Moser, L.↗