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At least 91 records · Page 5

High performance ammonium nitrate propellant

A high performance propellant having greatly reduced hydrogen chloride emission is presented. It is comprised of: (1) a minor amount of hydrocarbon binder (10-15%), (2) at least 85% solids including ammonium nitrate as the primary oxidizer (about 40% to 70%), (3) a significant amount (5-25%) powdered metal fuel, such as aluminum, (4) a small amount (5-25%) of ammonium perchlorate as a supplementary oxidizer, and (5) optionally a small amount (0-20%) of a nitramine.

Anderson, F. A.↗

Influence of peroxyacetyl nitrate (PAN) on odd nitrogen in the troposphere and lower stratosphere

Nonmethane hydrocarbon breakdown in the atmosphere produces aldehydes of which a fraction are transferred into peroxyacetyl nitrates (PAN) in the presence of NO and NO2. Since ethane is destroyed photochemically primarily above 1 km, PAN can be introduced into the upper troposphere and lower stratosphere without the need to be transported from the boundary layer where most hydrocarbons are destroyed and where PAN may be lost due to thermal decomposition and heterogeneous loss. Mixing ratios of ethane in the lower troposphere increase by a factor of 4-8 from equatorial to northern mid-latitudes. This difference is directly translatable into a PAN latitude gradient. At mid-latitudes the concentration of PAN below 20 km is 0.1 ppb comparable to and in some instances larger than predicted HO2NO2 mixing ratios. Like HO2NO2 and HNO3, PAN serves as a reservoir for odd nitrogen.

Aikin, A. C.↗

Global distribution of peroxyacetyl nitrate

Peroxyacetyl nitrate (PAN) atmospheric concentration samples were collected hourly from an ocean vessel 50 mi off the continental coast traveling from Seattle to Chile in 1984. Air concentration data for PAN and light hydrocarbons (LHC) were also taken by aircraft in the same period over Wyoming and Colorado and over the eastern Pacific. The PAN concentrations were higher and more variable in the Northern Hemisphere than in the Southern Hemisphere, increased with altitude, and were higher in the winter than in summer. The summer PAN concentrations were higher in the continental troposphere than in the marine troposphere. The results show that photochemical models of the atmosphere which do not account for the reaction between nonmethane hydrocarbons and PAN will probably overestimate the abundances of NO(x) and HNO3. The collection of further PAN concentration data is recommended as a means to characterizing the moderating role of PAN in the photochemistry of the troposphere.

Singh, H. B.↗

Long term exposure of metals to hydrazine nitrate blend

A long term testing program is being conducted to determine the effects of materials in contact with a hydrazine nitrate blend for the purpose of designing chemical propulsion systems which can be used for current as well as future planetary spacecraft. Analysis of this data indicates that some aluminum alloys are acceptable for use with the particular blend of fuel used. Titanium alloy was identified as being acceptable for 10-year applications. Corrosion resistant steels, however, were found to have excessive corrosion rates and are therefore considered unacceptable for long-term use. There is also some evidence that the propellant decomposed at a rate far in excess of the acceptable rate of 0.1 percent per year when in contact with stainless steel.

Moran, Clifford M.↗

Observation of several chlorine nitrate (ClONO2) bands in stratospheric infrared spectra

Four of the most prominent and sharpest infrared absorption features of chlorine nitrate at 780.2, 807.7, 809.4, and 1292.6/cm have been observed in a series of infrared solar spectra obtained at an unapodized spectral resolution of 0.01/cm, using the Atmospheric Trace Molecule Spectroscopy instrument from on-board Sapcelab 3. A quantitative analysis of the nu4 Q branch at 780.2/cm has provided insight into the concentration of ClONO2 between 19 and 40 km altitude. While the mean profile deduced from three sunset occultations near 30 deg N latitude exhibits a shape close to that predicted by model calculations, its concentrations in the 20 to 32 km altitude range are, however, about 30 percent larger, reaching a peak concentration of 9 x 10 to the 8th molecules/cu cm at 25 km. The concentrations above 32 km, deduced from one sunrise occultation at 47 deg JS, are even larger than the corresponding sunset values at 30 deg N latitude. Some of these discrepancies may be caused by the rather large uncertainty in the assumed Q branch strength.

Zander, R.↗

Reactions of chlorine nitrate with HCl and H2O

The kinetics of the reactions of chlorine nitrate with HCl and H2O are characterized using a static photolysis/Fourier transform infrared spectrophotometer apparatus. For the homogeneous gas-phase reaction with HCl, an upper limit for the rate constant of less than 8.4 x 10 to the -21st, and for the reaction with H2O, a limit of less than 3.4 x 10 to the -21st cu cm/molecule per s, were obtained at 296 + or - 2 K. The yield of HNO3 is almost unity in both cases, and no synergistic effect is noted between HCl and H2O. The kinetic behavior of the reaction with H2O is well described by simple first-order kinetics, while the behavior of the reaction with HCl is described in terms of the Langmuir adsorption isotherm.

Hatakeyama, Shiro↗

Antarctic stratospheric chemistry of chlorine nitrate, hydrogen chloride, and ice - Release of active chlorine

The reaction rate between atmospheric hydrogen chloride (HCl) and chlorine nitrate (ClONO2) is greatly enhanced in the presence of ice particles; HCl dissolves readily into ice, and the collisional reaction probability for ClONO2 on the surface of ice with HCl in the mole fraction range from about 0.003 to 0.010 is in the range from about 0.05 to 0.1 for temperatures near 200 K. Chlorine is released into the gas phase on a time scale of at most a few milliseconds, whereas nitric acid (HNO3), the other product, remains in the condensed phase. This reaction could play an important role in explaining the observed depletion of ozone over Antarctica; it releases photolytically active chlorine from its most abundant reservoir species, and it promotes the formation of HNO3 and thus removes nitrogen dioxide from the gas phase. Hence it establishes the necessary conditions for the efficient catalytic destruction of ozone by halogenated free radicals.

Molina, Mario J.↗

Reaction of chlorine nitrate with hydrogen chloride and water at Antarctic stratospheric temperatures

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO2) with H2O and HCl on surfacers that simulate polar stratospheric clouds are studied at temperatures relevant to the Antarctic stratosphere. The gaseous products of the resulting reactions, HOCl, Cl2O, and Cl2, could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the additional formation of condensed-phase HNO3 could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.

Tolbert, Margaret A.↗

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

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.

Tolbert, Margaret A.↗

Direct observation of ClO from chlorine nitrate photolysis

Chlorine nitrate photolysis has been investigated with the use of a molecular beam technique. Excitation at both 248 and 193 nanometers led to photodissociation by two pathways, ClONO2 yields ClO + NO2 and ClONO2 yields Cl + NO3, with comparable yields. This experiment provides a direct measurement of the ClO product channel and consequently raises the possibility of an analogous channel in ClO dimer photolysis. Photodissociation of the ClO dimer is a critical step in the catalytic cycle that is presumed to dominate polar stratospheric ozone destruction. A substantial yield of ClO would reduce the efficiency of this cycle.

Minton, Timothy K.↗

Chloryl nitrate - A novel product of the OClO + NO3 + M recombination

The products of the reaction of OClO with NO3 were investigated between 220 and 298 K using a flow reactor and infrared, visible, and ultraviolet analysis. At temperatures below 250 K new infrared and ultraviolet absorption features were observed and assigned to the novel compound chloryl nitrate (O2ClONO2). Additionally, ClO and NO2 were observed as reaction products, indicating the existence of a second reaction channel. O2ClONO2 formation predominates at temperatures below 230 K. The reaction rate constant at 220 K is estimated to be on the order of 10 exp -14 cu cm/molecule s in 1-5 Torr of helium. These observations suggest that O2ClONO2 may exist in the terrestrial stratosphere.

Friedl, Randall R.↗

Development of an iron nitrate resistant injector valve for the Space Shuttle orbiter primary thruster

Design of a direct-acting valve (DAV) for a primary thruster which is fully interchangeable with a thruster equipped with pilot-operated valves is described. The DAV is based on a bellows to isolate propellants form the actuator for maximum resistance to iron nitrate and other contamination and to select optimum materials for the actuator. It provides improved seal performance under all operating conditions and insensitivity to pressure transients. As compared with the existing pilot-operated valve, the DAV design is much simpler, consists of fewer parts, and will be lower in cost.

Wichmann, Horst↗

Profiles of stratospheric chlorine nitrate (ClONO2) from atmospheric trace molecule spectroscopy/ATLAS 1 infrared solar occultation spectra

Stratospheric volume mixing ratio profiles of chlorine nitrate (ClONO2) have been retrieved from 0.01/cm resolution infrared solar occultation spectra recorded at latitudes between 14 deg N and 54 deg S by the atmospheric trace molecule spectroscopy Fourier transform spectrometer during the Atmospheric Laboratory for Applications and Science (ATLAS) 1 shuttle mission (March 24 to April 2, 1992). The results were obtained from nonlinear least squares fittings of the ClONO2 nu(sub 4) band Q branch at 780.21/cm with improved spectroscopic parameters generated on the basis of recent laboratory work. The individual profiles, which have an accuracy of about +/- 20%, are compared with previous observations and model calculations.

Rinsland, C. P.↗

Production of NO2 from Photolysis of Peroxyacetyl Nitrate

Peroxyacetyl nitrate (PAN) vapor was photolyzed at 248 nm, and the NO2 photoproduct was detected by laser-induced fluorescence. The quantum yield for the production of NO2 from PAN photolysis was determined by comparison to HNO3 photolysis data taken under identical experimental conditions. The average of data collected over a range of total pressures, precursor concentrations, and buffer gases was 0.83 +/- 0.09 for the NO2 quantum yield, where the statistical uncertainty is 2 standard deviations.

Mazely, Troy L.↗

Construction of a Specialized Cloning Strain of E. Coli for the Nitrate Reductase Genes of Haloferax Denitrificans

This is the final report on Joint Research Interchange (NCC2-5011) "Construction of a Specialized Cloning Strain of E.. coli for the Nitrate Reductase Genes of Haloferax denitrificans." Originally the award was 11/l/93-10/31/95, but there were no-cost extensions made, because of a year Sabbatical at the Pasteur Institute in Paris and other leaves of 3 months each at the Pasteur Institute, during which work could not be done on this project, which extended the closing date to 10/30/98.

Johnson, Emmett↗

Pressure-Dependent Yields and Product Branching Ratios in the Broadband Photolysis of Chlorine Nitrate

The photolysis of chlorine nitrate was studied using broadband flash photolysis coupled with long-path ultraviolet-visible absorption spectroscopy. Branching ratios for the Cl + NO3 and ClO + NO2 product channels were determined from time-dependent measurements of ClO and NO3 concentrations. Yields of the ClO and NO3 products displayed a dependence on the bath gas density and the spectral distribution of the photolysis pulse. Product yields decreased with increasing bath gas density regardless of the spectral distribution of the photolysis pulse; however, the decrease in product yield was much more pronounced when photolysis was limited to longer wavelengths. For photolysis in a quartz cell (lambda > 200 nm) the yield decreased by a factor of 2 over the pressure 10-100 Torr. In a Pyrex cell (lambda > 300 nm), the yield decreased by a factor of 50 over the same pressure range. When photolysis was limited to lambda > 350 nm, the yield decreased by a factor of 250. Branching ratios for the photolysis channels [ClONO2 + h.nu yields ClO + NO2 (1a) and ClONO2 + h.nu yields Cl + NO3 (lb)] were determined from the relative ClO and NO3 product yields at various pressures. Although the absolute product yield displayed a pressure dependence, the branching between the two channels was independent of pressure. The relative branching ratios (assuming negligible contributions from other channels) are 0.61 +/- 0.20 for channel 1a and 0.39 +/- 0.20 for channel lb for photolysis with lambda > 200 nm and 0.44 +/- 0.08 for channel 1a and 0.56 +/- 0.08 for channel 1b for photolysis with lambda > 300 nm. The implications of these results for the chemistry of the lower stratosphere are discussed.

Nickolaisen, Scott L.↗

Complex Refractive Index of Ammonium Nitrate in the 2-20 micron Spectral Range

Using high resolution Fourier Transform Infrared Spectroscopy (FTIR) absorbance/transmittance spectral data for ammonium sulfate (AMS), calcium carbonate (CAC) and ammonium nitrate (AMN), comparisons were made with previously published complex refractive indices data for AMS and CAC to infer experimental parameters to determine the imaginary refractive index for AMN in the infrared wavelength range from 2 to 20 microns. Kramers-Kronig mathematical relations were applied to calculate the real refractive index for the three compositions. Excellent agreement for AMS and CAC with the published values was found, validating the complex refractive indices obtained for AMN. Backscatter calculations using a lognormal size distribution for AMS, AMN, and CAC aerosols were performed to show differences in their backscattered spectra.

Jarzembski, Maurice A.↗