Infrared spectral studies of peroxyacetyl nitrate /PAN/
Peroxyacetyl nitrate decomposition products under continued and discontinued irradiations determined by IR spectral analysis
Fild, I.↗
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Dynamic Nuclear Polarization in Samarium Doped Lanthanum Magnesium Nitrate
The dynamic nuclear polarization of hydrogen nuclei by the solid effect in single crystals of samarium doped lanthanum magnesium nitrate (Sm:LMN) was studied theoretically and experimentally. The equations of evolution governing the dynamic nuclear polarization by the solid effect were derived in detail using the spin temperature theory and the complete expression for the steady state enhancement of the nuclear polarization was calculated. Experimental enhancements of the proton polarization were obtained for eight crystals at 9.2 GHz and liquid helium temperatures. The samarium concentration ranged from 0.1 percent to 1.1 percent as determined by X-ray fluorescence. A peak enhancement of 181 was measured for a 1.1 percent Sm:LMN crystal at 3.0 K. The maximum enhancements extrapolated with the theory using the experimental data for peak enhancement versus microwave power and correcting for leakage, agree with the ideal enhancement (240 in this experiment) within experimental error for three of the crystals.
Byvik, C. E.↗
On charged particle tracks in cellulose nitrate and Lexan
Investigations were performed aimed at developing plastic nuclear track detectors into quantitative tools for recording and measuring multicharged, heavy particles. Accurate track etch rate measurements as a function of LET were performed for cellulose nitrate and Lexan plastic detectors. This was done using a variety of incident charged particle types and energies. The effect of aging of latent tracks in Lexan in different gaseous atmospheres was investigated. Range distributions of high energy N-14 particle bevatron beams in nuclear emulsion were measured. Investigation of charge resolution and Bragg peak measurements were carried out using plastic nuclear track detectors.
Benton, E. V.↗
Negative ion spectrometry for detecting nitrated explosives
Ionization procedure is modified to produce mainly negative ions by electron capture. Peaks of negative ions are monitored conventionally. Nitrated organic materials could be identified directly from sample sniff inlet stream by suitably modified mass spectrometer because of unique electronegativity which nitro group imparts to organic material.
Boettger, H. G.↗
High resolution infrared absorptivities for gaseous chlorine nitrate
High resolution infrared absorptivities of chlorine nitrate (ClONO2) are required in order to quantitatively evaluate, by examination of infrared spectra obtained recently from balloon-borne spectrometers, the possible occurrence of this compound in the stratosphere. In the present study, infrared absorptivities for four absorption bands of gaseous ClONO2 have been measured at 0.0625 per cm spectral resolution with a Fourier transform infrared (FT-IR) system. Spectra were obtained at two pressures (0.05 and 1.05 torr) of pure ClONO2 and with 125 torr of N2 added to a 0.50 torr sample. Absorptivities for a range of spectral resolutions (0.0625, 0.125, 0.25 and 0.50 per cm) have been calculated from the data.
Graham, R. A.↗
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.↗
Utilization of urea, ammonia, nitrite, and nitrate by crop plants in a Controlled Ecological Life Support System (CELSS)
The utilization of nitrogen compounds by crop plants is studied. The selection of crop varieties for efficient production using urea, ammonia, nitrite, and nitrate, and the assimilation of mixed nitrogen sources by cereal leaves and roots are discussed.
Huffaker, R. C.↗
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↗