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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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NASA NTRS1984

s-wave threshold in electron attachment - Results in 2-C4F6 and CFCl3 at ultra-low electron energies

Electron attachment lineshapes and cross sections are reported for the processes 2-C4F6(-)/2-C4F6 and Cl(-)/CFCl3 at electron energies of 0-120 and 0-140 meV, and at resolutions of 6 and 7 meV (FWHM), respectively. As in previous measurements in CCl4 and SF6, the results show resolution-limited narrow structure in the cross section at electron energies below 15 meV. This structure arises from the divergence of the s-wave cross section in the limit of zero electron energy. Comparisons are given with swarm-measured results, and with collisional ionization (high-Rydberg attachment) data in this energy range.

Chutjian, A.↗
NASA NTRS1986

Atmospheric trace gases - Trends and distributions over the last decade

Concentrations of the halocarbons CCl3F (F-11), CCl2F2 (F-12), CCl4, and CH3CCl3, methane (CH4), and nitrous oxide (N2O) over the decade between 1975 and 1985 are reported, based on measurements taken every January at the South Pole and in the Pacific Northwest. The concentrations of F-11, F-12, and CH3CCl3 in both hemispheres are now more than twice their concentrations 10 years ago. However, the annual rates of increase of F-11, F-12, and CH3CCl3 are now considerably slower than earlier in the decade, reflecting in part the effects of a ban on their nonessential uses. Continued increases in these trace gas concentrations may warm the earth and deplete the stratospheric ozone layer, which may cause widespread climatic changes and affect global habitability.

Rasmussen, R. A.↗
NASA NTRS1987

An intercomparison technique for measuring thermal attachment cross sections and rate constants in distinct final channels

A new technique is introduced for comparing negative-ion signal rates in which a common ion is produced by dissociative attachment in a series of molecules. Measurements are carried out at electron energies less than 100 MeV and at resolutions of 6-8 MeV (FWHM). The technique is demonstrated by detection of the Cl(-) signal in CFCl3, CCl4, CF2Cl2, 1,1,2-C2Cl3F3, 1,1,1-C2Cl3F3 and C2Cl4. Measurements for 1,1,1-C2Cl3F3 show that there is a significant open channel, other than Cl(-) formation, which accounts for about 60 percent of negative-ion formation in thermal-multiple-collision (swarm) experiments. Channel cross sections and rate constants are given for the process Cl(-)/1,1,1-Cl2Cl3F3, as well as in C2Cl4, for the separate channels Cl(-)/C2Cl4 and C2Cl4(-)/C2Cl4.

Alajajian, S. H.↗
NASA NTRS1987

Infrared spectroscopic measurements of halogenated source gases in the stratosphere with the ATMOS instrument

The volume mixing ratios of the six most important halogenated source species (CH3Cl, CF2Cl2, CFCl3, CHF2Cl, CCl4, and CF4) have been retrieved over the 10- to 30-km altitude range from the analysis of 0.01/cm resolution infrared solar occultation spectra recorded near 30 deg N and 47 deg S latitudes with the ATMOS (Atmospheric Trace Molecule Spectroscopy) instrument, operating from on board Spacelab 3 (April-May 1985). The results reported here, although in satisfactory agreement with recent in situ values obtained from air sampling techniques, are limited in accuracy by the limited absorption representative of most of the species and by uncertainties in the spectroscopic parameters currently available for these gases. They demonstrate, however, the power of the IR remote sensing approach for evaluating on a global scale the total chlorine budget of the atmosphere, and they provide an independent set of simultaneous data acquired for the important source and reservoir halogenated molecular species in the upper atmosphere.

Zander, R.↗
NASA NTRS1987

Fluorescence yields from photodissociative excitation of chloromethanes by vacuum ultraviolet radiation

The photoabsorption and fluorescence cross sections of chloromethanes were measured in the 105-220 nm region using synchrotron radiation as a light source. The fluorescence threshold for CCl4 is at 152 nm with a maximum yield of 3 percent at 113 nm. The fluorescence results from the CCl2(A-X) system. For CHCl3, the fluorescence threshold is at 155 nm with a maximum yield of 0.6 percent at 110 nm. For CH2Cl2, the threshold is at 137 nm with a maximum yield of 0.35 percent at 107 nm. The fluorescence yield of CH3Cl is very small with an upper limit of 0.02 percent. The photodissociation processes are discussed in accord with the fluorescence data observed. Vibrational structures in CHCl3 and CH3Cl2 are observed and classified into progressions.

Lee, L. C.↗
NASA NTRS1988

Effect of computed horizontal diffusion coefficients on two-dimensional N2O model distributions

The effects of horizontal diffusion coefficients K(yy) and K(yz), computed directly from the residual circulation, on the N2O distribution in a photochemical model were investigated, using a modified version of the two-dimensional model of Guthrie et al. (1984). The residual circulation was computed using the NMC's temperature data and the heating rates reported by Rosenfield et al. (1987). As compared with the effect of the residual circulation alone, the use of horizontal diffusion coefficients produced substantial changes in the N2O distribution and increased the N2O's lifetime values by a few percent. It is suggested that trace gases, such as CH4, CFCl3, CF2Cl2, CH3Cl, and CCl4, which impact the NO(x), HO(x), and Cl(x) radical distributions and therefore ozone, will be influenced in a similar manner by the addition of more realistic diffusion fields.

Jackman, Charles H.↗
NASA NTRS1988

Mixing ratios of trace gases in the austral polar atmosphere during August and September of 1987

Mixing ratios are presented for a number of long-lived trace gases in the austral polar atmosphere during August and September of 1987. The recent discovery of a 12-year trend of increasing depletion of ozone over the Antarctic Continent in the spring of each year led to numerous theoretical interpretations and several scientific expeditions to the region. The results herein were obtained as part of a major effort involving penetration of the region of ozone depletion by NASA's multi-instrumented aircraft. One of the 14 instruments on the high-altitude ER-2 aircraft collected pressurized air samples between latitudes of 53 degrees and 72 degrees south at pressure altitudes up to 21 km in a series of 12 flights from Punta Arenas, Chile, over the Palmer Peninsula. The sampling system, located in the nose section of ER-2, has an inlet tube in the free airstream, a metal-bellows air pump, and 14 specially treated 1.6 l stainless-steel canisters for containing the pressurized air at 350 kPa. A typical flight profile consisted of a southbound path on the 428 K potential temperature surface, a descent to a pressure altitude of 13.7 km, a climb to the 460 K surface, and return on this surface. Mixing ratios for the trace gases were obtained from gas chromatographic analyses of the pressurized air samples. Of the species measured, the mixing ratios for CH4, CO, N2O, CF2 Cl2, CFCl3, CH3, CCl3, CCl4, and C2F3Cl3 are reported here.

Vedder, James F.↗
NASA NTRS1988

Observations of stratospheric source gas profiles during the Arctic winter

An international campaign was performed at ESRANGE rocket base, near Kiruna, Sweden (68 N) from January 4 to February 15 in order to investigate the Chemistry of Ozone in the Polar Stratosphere (CHEOPS). Within the framework of this campaign two sets of large stratospheric air samples were collected by means of a balloon borne cryogenic air sampler. The two balloons were launched on February 1, and February 10, 1988. At present the samples are analyzed in our laboratory for their contents of several long lived trace gases such as CH4, N2O, H2, CO2, CO and the major halocarbons CH3Cl, CFCl3, CF2Cl2, CCl4, CH3CCl3, and C2F3Cl3. The vertical profiles derived from these samples will be presented and compared with previous observations made in February 1987. The data will be discussed in view of the dynamical evolution of the Arctic polar vortex during this winter.

Schmidt, U.↗
NASA NTRS1989

Trace gases in the Antarctic Atmosphere

Whole-air samples collected aboard the NASA ER-2 and DC-8 aircraft as part of the Airborne Antarctic Ozone Experiment were analyzed in a field laboratory set up at Punta Arenas, Chile. Mixing ratios obtained from gas chromatographic analyses of these samples are presented for CH4, CO, N2O, CFCl3, CF2Cl2, C2F3Cl3, CH3CCl3, and CCl4. A comparison of CFCl3/N2O mixing ratios from the flights of September 16-29, 1987 provides evidence of sustained subsidence.

Heidt, L. E.↗
NASA NTRS1989

Transport into the south polar vortex in early spring

The effect of transport on the springtime decline in ozone in the southern polar vortex was investiated using data on long-lived gas tracers (N2O, CH4, CCl4, CH3CCl3, CO, CFC-11, CFC-12, and CFC-113) obtained by the ER-2 aircraft in the period between August 23 and September 22 during the Airborne Antarctic Ozone Experiment. It was found that, while the concentrations of long-lived trace gases remained relatively constant for fixed potential temperature and latitude, the ozone mixing ratio over the same period declined by more than 50 percent inside the polar vortex near 18-km altitude. These data indicate a substantial photochemical sink of ozone. The evidence of the zero or negative time tendencies for long-lived trace gases and the meridional and vertical gradients of ozone imply that transport is supplying ozone to the polar region during springtime.

Hartmann, D. L.↗
NASA NTRS1991

Cold plasma processing of local planetary ores for oxygen and metallurgically important metals

The utilization of a cold or nonequilibrium plasma in chlorination processing is discussed. Titanium dioxide (TiO2) was successfully chlorinated at temperatures between 700 and 900 C without the aid of carbon. In addition to these initial experiments, a technique was developed for determining the temperature of a specimen in a plasma. Development of that technique has required evaluating the emissivity of TiO2, ZrO2, and FeOTiO2 and analyzing the specimen temperature in a plasma as a function of both power absorbed by the plasma and the pressure of the plasma. The mass spectrometer was also calibrated with TiCl4 and CCl4 vapor.

Lynch, D. C.↗
NASA NTRS1989

Proposed reference models for CO2 and halogenated hydrocarbons

The vertical distribution of carbon dioxide, halocarbons and their sink products, HCl and HF, have become available, mainly by means of balloon measurements. Most measurements were made at northern mid-latutudes, but some constituents were measured at tropical latitudes and in the Southern Hemisphere as well. An attempt is made here to combine the available data for presentation of reference models for CO2, CCl4 CCl3F, CCl2F2, CClF3, CF4, CCl2F-CClF2, CClF2-CClF2, CClF2-CF3, CF3-CF3, CH3Cl, CHClF2, CH3-CCl3, CBrClF2, CBrF3, HCl and HF.

Fabian, P.↗
NASA NTRS1991

Thermodynamic models of the chemistry of lunar volcanic gases

Thermodynamic models and mass-balance arguments are used to constrain the chemistry of lunar volcanic gases. The results predict that lunar gases were dominated by reduced C and S gases such as CO, COS, CS2, S2. The more oxidized gases CO2 and SO2 were also important, but only in limited temperature ranges. Gases such as Cl2, CCl4, and CF4 were more abundant than HF and HCl, which were the two major H compounds in the lunar gases. Chlorides and fluorides were important species for transporting many volatile and ore-forming metals, and the implications for fractionating and concentrating metals into lunar ore-deposits merit further study.

Fegley, Bruce, Jr.↗
NASA NTRS1992

The chlorine budget of the present-day atmosphere - A modeling study

The contribution of source gases to the total amount of inorganic chlorine (ClY) is examined analytically with a time-dependent model employing 11 source gases. The source-gas emission data are described, and the modeling methodology is set forth with attention given to the data interpretation. The abundances and distributions are obtained for all 11 source gases with corresponding ClY production rates and mixing ratios. It is shown that the ClY production rate and the ClY mixing ratio for each source gas are spatially dependent, and the change in the relative contributions from 1950 to 1990 is given. Ozone changes in the past decade are characterized by losses in the polar and midlatitude lower stratosphere. The values for CFC-11, CCl4, and CH3CCl3 suggest that they are more evident in the lower stratosphere than is suggested by steady-state estimates based on surface concentrations.

Weisenstein, Debra K.↗
NASA NTRS1992

Absorption parameters of very dense molecular spectra for the HITRAN compilation

Cross sections for the heavy molecules CFC-11, CFC-12, CFC-13, CFC-14, CFC-22, CFC-113, CFC-114, CFC-115, CCl4, ClONO2, N2O5, HNO4, and HNO3 are included on the HITRAN 91 database. For many of these species, the cross sections vary by a factor of two between room temperature and temperatures near 210 K. The chemical importance of the heavy molecules, the quantitative accuracy of the HITRAN 91 cross sections, and the need for additional spectroscopic quantification are discussed.

Massie, S. T.↗
NASA NTRS1992

Electron attachment to molecules at ultralow electron energies

Experimental techniques, both single-collision and multiple-collision, for studying electron attachment to molecules at energies below 0.1 eV are reviewed. Recent attachment results in HI, DI, F2, SF6, CCl4, and CFCl3 are examined from the point of view of threshold behavior (s- or p-wave), threshold energetics, and the temperature dependence of the attachment rate constant. An interesting application of the s-wave phenomenon to trace-species detection is given.

Chutjian, Ara↗
NASA NTRS1994

Long term trend of selected halogenated hydrocarbons

The so-called 'Library of Background Air' at the Oregon Graduate Institute was used to determine the trend in volume mixing ratios of selected halogenated hydrocarbons in the time period 1977-1989. This library consists of background air samples most of them taken at Cape Meares (Oregon). For storage stainless steel containers are used. Tests have shown the gases under consideration to be stable in these containers. Analyses using a GC/MS-system were performed for the CFCs 11, 12, 12B1 (HALON 1211, CBrClF2), 22, 113, 114 and CH3Cl, CH3Br, CH3CCl3, CCl4. The advantage of this unique investigation: different aged air samples are analyzed at the same time with the same instrument. No calibrations or intercalibrations are needed. All data are presented in normalized mixing ratios versus time. We discuss the results, derive rate constants and present a formula to describe the nonlinear increases.

Borchers, R.↗
NASA NTRS1994

The MIPAS balloon borne trace constitutent experiment

A novel cryogenic Fourier transform spectrometer (FTS) has been developed for limb emission measurements in the mid IR-region from balloon-borne platforms. The FTS is a rapid scanning interferometer using a modified Michelson arrangement which allows a spectral resolution of 0.04 cm(exp -1) to be achieved. Solid carbon-dioxide cooling of the spectrometer and liquid-helium cooling of the detectors provide adequate sensitivity. The line of sight can be stabilized in terms of azimuth and elevation. A three-mirror off-axis telescope provides good vertical resolution and straylight rejection. Calibration is performed by high elevation and internal blackbody measurements. Four balloon flights were performed, two of them during spring turn-around 1989 and 1990 over mid-latitudes (Aire sur L'Adour, France, 44 deg N) and two near the northern polar circle in winter 1992 (Esrange, Sweden, 68 deg N). Limb emission spectra were collected from 32 km to 39 km floating altitudes covering tangent heights between the lower troposphere and the floating altitude. The trace gases CO2, H2O, O3, CH4, N2O, HNO3, N2O5, ClONO2, CF2Cl2, CFCl3, CHF2Cl, CCl4, and C2H6 have been identified in the measured spectra. The 1989 data have been analyzed to retrieve profiles of O3, HNO3, CFCl3 and CF2Cl2. The flights over Kiruna have provided the first ever reported profile measurements of the key reservoir species ClONO2 and N2O5 inside the polar vortex.

Oelhaf, H.↗