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At least 217 records · Page 12

Microwave spectra of van der Waals complexes of importance in planetary atmospheres

The Fourier-transform Fabry-Perot pulsed-molecular-beam microwave spectrometer at NIST was used to study the microwave spectra of a number of molecular dimers and trimers that may be present in planetary atmospheres. The weak van der Waals bonds associated with these species usually give rise to rotational-tunneling splittings in the microwave spectra. The microwave spectrum of the water dimer species was used to illustrate the complications that can arise in the study of the rotational spectra of these loosely bound species. In addition to the water dimer species, the microwave spectra of the following hydrogen-bonded and van der Waals complexes were studied: (CO2)2-H2O, CO2-(H2O)2, CO2-H2S, N2-H2O, CO-H2O, SO2-H2O, and O3-H2O.

Suenram, R. D.↗

Uranus photochemistry and prospects for Voyager 2 at Neptune

CH4 is the only photochemically active constituent in the atmospheres of Uranus and Neptune. NH3, H2O and H2S are all removed by condensation at pressures greater than 1.5 bars. Although the bulk mole fraction (about 2 percent) of CH4 is 20-30 times its solar value on both planets, it drops to its saturation limit (about 0.0001) at the Uranus tropopause, but remains high (about 2 percent) at the Neptune tropopause. This results in much greater mixing ratios of the product hydrocarbons in the stratosphere of Neptune. On both planets, the photolysis products of CH4 undergo condensation near the tropopause and the upper stratosphere. Voyager observations of the hydrocarbons at Uranus and those planned at Neptune are discussed, along with their implications for upper-atmospheric physics and thermochemistry.

Atreya, S. K.↗

Sulfur, ultraviolet radiation, and the early evolution of life

The present biosphere is shielded from harmful solar near ultraviolet (UV) radiation by atmospheric ozone. It is suggested that elemental sulfur vapor could have played a similar role in an anoxic, ozone-free, primitive atmosphere. Sulfur vapor would have been produced photochemically from volcanogenic SO2 and H2S. It is composed of ring molecules, primarily S8, that absorb strongly throughout the near UV, yet are expected to be relatively stable against photolysis and chemical attack. It is also insoluble in water and would thus have been immune to rainout or surface deposition over the oceans. Since the concentration of S8 in the primitive atmosphere would have been limited by its saturation vapor pressure, surface temperatures of 45 C or higher, corresponding to carbon dioxide partial pressures exceeding 2 bars, are required to sustain an effective UV screen. A warm, sulfur-rich, primitive atmosphere is consistent with inferences drawn from molecular phylogeny, which suggest that some of the earliest organisms were thermophilic bacteria that metabolized elemental sulfur.

Kasting, J. F.↗

Corrosion Prevention in Copper Combustion Chamber Liners of Liquid Oxygen/Methane Booster Engines

Prior research conducted by United Technologies Research Center and Rockwell International Rocketdyne Division encountered severe copper corrosion while flowing hydrocarbon fuels through copper cooling tubes. These experimental results have very important implications for the development of low-cost, regeneratively cooled, oxygen/hydrocarbon bipropellant booster engines. Aerojet TechSystems undertook a program sponsored by NASA/Lewis Research Center in 1986 with two objectives: (1) to define the corrosive interaction process that occurs between hydrocarbon fuels and copper combustion chamber liner materials, using both static and dynamic test methods, and (2) to identify and demonstrate protective measures against this corrosive process. The results of the first program task demonstrated that the most damaging corrosive process was caused by trace amounts of sulfur-containing impurities in the hydrocarbon fuel which react with the copper chamber liner material to form cuprous sulfide (Cu2S), as reported in Paper No. AlAA 88-3215. Experiments were conducted which demonstrated this corrosive process with Mil-Spec RP-1, propane, and methane fuels in contact with OFHC, NASA-Z, and ZrCu coppers. The preliminary results of the second program task demonstrated that electrodeposited gold and platinum coatings held promise of preventing corrosion of copper chamber liners by methane contaminated with sulfur-containing impurities, as reported in Paper No. AIAA 89-2738. Experiments were conducted which demonstrated greatly reduced corrosion of copper by hydrogen sulfide (H2S) and methyl mercaptan (CH3SH) as measured impurities in methane. This paper presents the concluding, confirmatory results from the second program task. The efficacy of a protective gold coating on NASA-Z copper cooling channel walls was conclusively demonstrated. Tests were conducted in the Aerojet Carbothermal Test Facility which provide realistic simulations of booster engine cooling channel conditions such as temperature, pressure, flow velocity, and heat flux. Dynamic test series were performed with methane containing 5 and 10 ppm (by volume) hydrogen sulfide. Gold-plated and unplated copper alloy specimens were evaluated. The tests demonstrated that gold coatings were effective in preventing corrosion of the copper. Posttest metallographic examinations of the unplated specimens showed severe corrosion as a result of reaction with the sulfur containing contaminant in the fuel. In contrast, posttest metallographic examination of the gold-coated specimens showed no corrosion under similar operating conditions. The findings from metallurgical and chemical analyses of the copper specimens, chemical analysis of the methane, and description of all test conditions are provided. Conclusions are reached as to the efficacy of the plating methods and the effectiveness of the metal coatings in the prevention of corrosion in hydrocarbon-fueled booster engine combustion chamber liners.

S D Rosenberg↗

Io's atmosphere from microwave detection SO2

The microwave detection of SO2 at 222 GHz in Io's atmosphere is reported. The observations imply an SO2 surface pressure of 4-35 nanobars, covering 3-15 percent of the surface on both leading and trailing sides of Io when illuminated by the sun. This supports atmospheric models in which the partial pressure of SO2 at the surface is determined by the Io surface temperature, favoring, in particular, the 'albedo cold-trap' models. The failure to detect H2S at 169 GHz suggests that the pressure of this gas is probably below 10 to the -10th bar. These results, taken together with Pioneer ionospheric data, suggest that an atmospheric gas other than SO2 is present. It is proposed that the locally buffered SO2 atmosphere coexists with a background atmosphere of oxygen with a partial surface pressure of about 20 nanobars.

Lellouch, Emmanuel↗

The atmosphere of Neptune - Results of radio occultation measurements with the Voyager 2 spacecraft

This paper presents the vertical temperature and composition profiles of Neptune's troposphere and stratosphere, covering an altitude of 250 km, obtained from radio tracking data that were acquired during Voyager-2's occultation by Neptune, which began near 62 deg N planetographic latitude and ended near 45 deg S latitude. In the computations, the He/H2 abundance ratio 15/85 was adapted, which is consistent with solar abundance estimates and with recent results from Uranus. It was assumed that aerosols and heavier gases such as CH4, NH3, H2S, and H2O have a negligible effect on the microwave refractivity above the 0.5 bar pressure level.

Lindal, G. F.↗

Laboratory evaluation and application of microwave absorption properties under simulated conditions for planetary atmospheres

Laboratory measurements of microwave and millimeter wave properties of the simulated atmosphere of the outer planets and their satellites has continued. One of the focuses is on the development of a radiative transfer model of the Jovian atmosphere at wavelengths from 1 mm to 10 cm. This modeling effort led to laboratory measurements of the millimeter wave opacity of hydrogen sulfide (H2S) under simulated Jovian conditions. Descriptions of the modeling effort, the Laboratory experiment, and the observations are presented. Correlative studies of measurements with Pioneer-Venus radio occultation measurements with longer wavelength emission measurements have provided new ways for characterizing temporal and spatial variations in the abundance of both gases H2SO4 and SO2, and for modeling their roles in the subcloud atmosphere. Laboratory measurements were conducted on 1.35 cm (and 13 cm) opacity of gaseous SO2 and absorptivity of gaseous SO2 at the 3.2 mm wavelength under simulated Venus conditions. Laboratory measurements were completed on millimeter wave dielectric properties of liquid H2SO4, in order to model the effects of the opacity of the clouds of Venus onto millimeter wave emission spectrum.

Steffes, Paul G.↗

Airborne sulfur trace species intercomparison campaign: Sulfur dioxide, dimethylsulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide

Results from an airborne intercomparison of techniques to measure tropospheric levels of sulfur trace gases are presented. The intercomparison was part of the NASA Global Tropospheric Experiment (GTE) and was conducted during the summer of 1989. The intercomparisons were conducted on the Wallops Electra aircraft during flights from Wallops Island, Virginia, and Natal, Brazil. Sulfur measurements intercompared included sulfur dioxide (SO2), dimethylsulfide (DMS), hydrogen sulfide (H2S), carbon disulfide (CS2), and carbonyl sulfide (OCS). Measurement techniques ranged from filter collection systems with post-flight analyses to mass spectrometer and gas chromatograph systems employing various methods for measuring and identifying the sulfur gases during flight. Sampling schedules for the techniques ranged from integrated collections over periods as long as 50 minutes to one- to three-minute samples every ten or fifteen minutes. Several of the techniques provided measurements of more than one sulfur gas. Instruments employing different detection principles were involved in each of the sulfur intercomparisons. Also included in the intercomparison measurement scenario were a host of supporting measurements (i.e., ozone, nitrogen oxides, carbon monoxide, total sulfur, aerosols, etc.) for purposes of: (1) interpreting results (i.e., correlation of any noted instrument disagreement with the chemical composition of the measurement environment); and (2) providing supporting chemical data to meet CITE-3 science objectives of studying ozone/sulfur photochemistry, diurnal cycles, etc. The results of the intercomparison study are briefly discussed.

Gregory, Gerald L.↗

Low temperature measurement of the vapor pressures of planetary molecules

Interpretation of planetary observations and proper modeling of planetary atmospheres are critically upon accurate laboratory data for the chemical and physical properties of the constitutes of the atmospheres. It is important that these data are taken over the appropriate range of parameters such as temperature, pressure, and composition. Availability of accurate, laboratory data for vapor pressures and equilibrium constants of condensed species at low temperatures is essential for photochemical and cloud models of the atmospheres of the outer planets. In the absence of such data, modelers have no choice but to assume values based on an educated guess. In those cases where higher temperature data are available, a standard procedure is to extrapolate these points to the lower temperatures using the Clausius-Clapeyron equation. Last summer the vapor pressures of acetylene (C2H2) hydrogen cyanide (HCN), and cyanoacetylene (HC3N) was measured using two different methods. At the higher temperatures 1 torr and 10 torr capacitance manometers were used. To measure very low pressures, a technique was used which is based on the infrared absorption of thin film (TFIR). This summer the vapor pressure of acetylene was measured the TFIR method. The vapor pressure of hydrogen sulfide (H2S) was measured using capacitance manometers. Results for H2O agree with literature data over the common range of temperature. At the lower temperatures the data lie slightly below the values predicted by extrapolation of the Clausius-Clapeyron equation. Thin film infrared (TFIR) data for acetylene lie significantly below the values predicted by extrapolation. It is hoped to bridge the gap between the low end of the CM data and the upper end of the TFIR data in the future using a new spinning rotor gauge.

Kraus, George F.↗

Laboratory studies of the newly discovered infrared band at 4705.2/cm (2.1253 microns) in the spectrum of Io - The tentative identification of CO2

The present evaluation of results from over 120 laboratory experiments relevant to the Trafton et al. (1991) discovery of a 2.1253-micron line in the spectrum of Io demonstrates that this band is produced by neither overtones nor combinations of the fundamental bands of molecules already noted on Io. Since the band's frequency is close to the first overtone of the nu(3) asymmetric stretching mode of CO2, attention is given this molecule's behavior under Io conditions. While pure solid CO2, and CO2 intimately mixed in a matrix of solid SO2 and H2S, generate bands of similar widths, these fall at frequencies lower than the Io band. Attention is given to the possible identification of the Io band with CO2 multimers of 'clusters' on Io.

Sandford, Scott A.↗

Interpretation of the ion mass spectra in the mass per charge range 25-35 amu/e obtained in the inner coma of Halley's comet by the HIS-sensor of the Giotto IMS experiment

The IMS-HIS double-focusing mass spectrometer that flew on the Giotto spacecraft covered the mass per charge range from 12 to 56 (amu/e). By comparing flight data, calibration data and results of model calculations of the ion population in the inner coma, the absolute mass scale is established, and ions in the mass range 25 to 35 are identified. Ions resulting from protonation of molecules with high proton affinity are relatively abundant, enabling us to estimate relative source strengths for H2CO, CH3OH, HCN, and H2S, providing for the first time a positive in situ measurement of methanol. Also, upper limits for NO and some hydrocarbons are derived.

Geiss, J.↗

Io's volcanic and sublimation atmospheres

Fully 3D axisymmetric gasdynamic equations simulating SO2 and H2S frost sublimation and SO2 dayside and nightside volcanic atmospheres on Io are numerically solved, using a time-explicit finite-volume formulation. Both the sublimation and volcanic atmospheres generate horizontal supersonic winds away from the subsolar point or the volcanic vent. While the sublimation atmosphere is primarily driven by horizontal pressure gradients determined by surface temperatures, the volcanic atmosphere is driven by pressure gradients that are determined by the source rate. Sublimation and condensation produce patterns of surface deposits which are characteristic of the two types of atmospheres. The volcanic model is quantitatively consistent with Voyager observations of ring deposits.

Moreno, Miguel A.↗

Regenerative Cu/La zeolite supported desulfurizing sorbents

Efficient, regenerable sorbents for removal of H2S from fluid hydrocarbons such as diesel fuel at moderate condition comprise a porous, high surface area aluminosilicate support, suitably a synthetic zeolite, and most preferably a zeolite having a free lattice opening of at least 6 Angstroms containing from 0.1 to 0.5 moles of copper ions, lanthanum ions or their mixtures. The sorbent removes sulfur from the hydrocarbon fuel in high efficiency and can be repetitively regenerated without loss of activity.

Voecks, Gerald E.↗

SO and SO2 in mass-loss envelopes of red giants - Probes of nonequilibrium circumstellar chemistry and mass-loss rates

SO emission was searched for in one or more of four transitions toward 23 oxygen-rich red giant or supergiant stars and one S star, selected primarily on the basis of their nonmaser SiO emission. SO was detected in a total of 14 circumstellar envelopes, 13 of which are new detections. The circumstellar abundance of SO (and SO2) is significantly enhanced over the equilibrium value achieved in the photospheres of these stars. In general, the SO abundances are significantly larger than predicted by nonequilibrium circumstellar chemistry models. Sulfur cannot be significantly depleted onto circumstellar grains, and probably exists as H2S (and/or SH) in the inner regions of the envelopes. The SO rotational-level population in most circumstellar envelopes observed is characterized by excitation temperatures less than or approximately equal to 50 K. The circumstellar abundance of SO2 is comparable to, or larger than, that of SO, ruling out the 'large' value adopted for the unshielded photodissociation rate for SO2 in recent models.

Sahai, Raghvendra↗

Neptune atmospheric probe mission

A feasibility study of a 'Galileo-like' atmospheric probe mission to Neptune aimed at obtaining in situ measurements of atmospheric and cloud composition and structure is presented. The main scientific desire is to obtain in situ measurements down to a pressure level of 75-100 bars to completely penetrate the CH4, NH3, H2S, NH4SH, and H2O clouds. The probe mission should be based on a Galileo complement of instruments with the addition of a gas chromatograph. Particular attention is given to the deployment design, and operation of the atmospheric entry probe system to accomplish the above mission objective.

Swenson, Byron L.↗

The structure, stability, and global distribution of Io's atmosphere

The paper reports on high-resolution millimeter-wave spectroscopic observations of Io carried out in 1990 and 1991 which allowed the first unambiguous ground-based detection of SO2 in Io's atmosphere. A reassessment of the IRIS-Voyager observations of the nu3 band of SO2 is presented, and it is shown that non-LTE effects are important in the formation of this band. It is thus concluded that the global SO2 atmosphere observed from earth has characteristics (pressure, temperature) similar to those observed at Loki by Voyager. The paper concludes with a simple thermal model of Io's lower atmosphere and a discussion of new upper limits that can be placed on the presence of H2S, SO, and CO in Io's atmosphere.

Lellouch, Emmanuel↗

Interpretation of the ion mass spectra in the mass range 25-35 obtained in the inner coma of Halley's comet by the HIS-sensor of the Giotto IMS Experiment

The IMS-HIS double-focussing mass spectrometer that flew on the Giotto spacecraft covered the mass per charge range from 12 to 56 (AMU/e). By comparing flight data, calibration data, and results of model calculations of the ion population in the inner coma, the absolute mass scale is established, and ions in the mass range 25 to 35 are identified. Ions resulting from protonation of molecules with high proton affinity are relatively abundant, enabling us to estimate relative source strengths for H2CO, CH3OH, HCN, and H2S, providing for the first time a positive in situ measurement of methanol. Also, upper limits for NO and some hydrocarbons are derived.

Geiss, J.↗

Observations of cometary parent molecules with the IRAM radio telescope

Several rotational transitions of HCN, H2S, H2CO, and CH3OH were detected in comets P/Brorsen-Metcalf 1989 X, Austin (1989c1) and Levy (1990c) with the Institute for Millimeter Radioastronomy (IRAM) 30-m radio telescope. This allows us to determine the production rates of these molecules and to probe the physical conditions of the coma.

Colom, P.↗