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Oligoglyceric acid synthesis by autocondensation of glyceroyl thioester

The autocondensation of the glyceroyl thioester, S-glyceroyl-ethane-thiol, yielded olioglyceric acid. The rates of autocondensation and hydrolysis of the thioester increased from pH 6.5 to pH 7.5 in 2,6-lutidine and imidazole buffers. Autocondensation and hydrolysis were much more rapid in imidazole buffers as compared to 2,6-lutidine and phosphate buffers. The efficiency of ester bond synthesis was about 20 percent for 40 mM S-glyceroyl-ethane-thiol in 2,6-lutidine and imidazole buffers near neutral pH. The size and yield of the olioglyceric acid products increased when the concentration of the thioester was increased. The relationship of these results to prebiotic polymer synthesis is discussed.

Weber, Arthur L.↗

Thermal evolution of Titan's atmosphere

The present model of Titan's atmosphere/surface evolution assumes the presence of a kilometer-deep ethane-methane ocean at the surface that serves as a tropospheric thermal balance-determining atmospheric-gas reservoir. The evolution of the atmospheric thermal structure is driven by gas-abundance changes occurring as stratospheric photolysis irreversibly converts methane into higher hydrocarbons, whereby the ocean becomes ethane-enriched and methane-depleted. A family of evolution models is presented whose various members correspond to different present-day ocean compositions, various atmospheric hydrogen abundances, and different schemes for frequency-averaging the gas opacity. A slow evolution over several billion years is envisioned.

Lunine, Jonathan I.↗

Titan

Saturn's satellite Titan is the second-largest in the solar system. Its dense atmosphere is mostly molecular nitrogen with an admixture of methane, a surface pressure of 1.5 bars and a surface temperature of 94K. The fundamental driving force in the long-term evolution of Titan's atmosphere is the photolysis of methane in the stratosphere to form higher hydrocarbons and aerosols. The current rate of photolysis and undersaturation of methane in the lower troposphere suggests the presence of a massive ethane-methane-nitrogen ocean. The ocean evolves to a more ethane-rich state over geologic time, driving changes in the atmospheric thermal structure. An outstanding issue concerning Titan's earliest history is the origin of atmospheric nitrogen: was it introduced into Titan as molecular nitrogen or ammonia? Measurement of the argon-to-nitrogen ratio in the present atmosphere provides a diagnostic test of these competing hypotheses. Many of the questions raised by the Voyager encounters about Titan and its atmosphere can be adequately addressed only by an entry probe, such as that planned for the Cassini mission.

Lunine, Jonathan I.↗

Radar reflectivity of Titan

The low dielectric constant of the liquid hydrocarbon and ethane-methane surface mixture of Titan has as a direct consequence a set of unique microwave-reflection properties which were sought out at 3.5-cm wavelength, using a 70-m transmitting antenna in conjunction with the VLA as a receiving instrument. The statistically significant echoes obtained indicate that Titan is not covered with a deep global ocean of ethane. A global ocean as shallow as about 200 m would have exhibited reflectivities smaller by an order of magnitude, and below the experiment's detection limit.

Muhleman, Duane O.↗

Long Duration Exposure Facility (LDEF) low-temperature Heat Pipe Experiment Package (HEPP)

The flight test results are discussed obtained with the Heat Pipe Experiment Package (HEPP). The HEPP was designed to demonstrate the performance of an ethane constant conductance heat pipe (CCHP) and an ethane heat pipe diode in microgravity. These heat pipes have a nominal operating temperature range of 140 to 250 K. Also, included in the HEPP is a Phase Change Material (PCM) canister which provides temperature stability through melting and freezing of the n-heptane PCM. A comparison of pre-flight, flight, and post-flight thermal performance is also presented.

Mcintosh, Roy↗

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Napier, Mary E.↗

Hypersonic ignition and thrust production in a scramjet

Experimental results are given for the specific impulse produced by a two-dimensional scramjet at flight speeds ranging between 2.5 and 5.5 km/s with a combustion chamber Mach number of 4.5. Both hydrogen and ethane fuels were used. Results show that provided sufficiently high pressures and sufficiently long combustion chambers are used specific impulses in excess of 1500 s can be obtained with hydrogen. Ethane produced specific impulses less than 600 s with the same conditions and model configuration.

Paull, A.↗

A Spectral Atlas of the Nu(sub 12) Fundamental of (13)C(12)CH6 in the 12 Micron Region

The recent discovery of the minor isotopomer of ethane, (13)C(12)CH6, in the planetary atmospheres of Jupiter and Neptune, added ethane to the molecules which can be used to determine isotopic (12)C(12)C ratios for the jovian planets. The increased spectral resolution and coverage of the IR and far-IR instruments to be carried on the Cassini mission to Saturn and Titan may enable the detection of the minor isotopomer. Accurate frequency and cross-section measurements of the nu(sub 12) fundamental under controlled laboratory condition are important to interpret current and future planetary spectra. High resolution spectra of the minor isotopomer (13)C(12)CH6 have been recorded in the 12.2 micron region using the Kitt Peak Fourier Transform (FTS) and the Goddard Tunable Diode Laser spectrometer (TDL). In a global fit to 19 molecular constants in a symmetric top Hamiltonian, transition frequencies of the nu(sub 12) fundamental ranging up to J=35 and K=20 have been determined with a standard deviation of less than 0.0005 cm(exp -1). From selected line intensity measurements, a vibrational dipole moment for the nu(sub 12) fundamental has been derived. Observed and calculated spectra covering the region from 740 cm(exp -1) and to 910 cm(exp -1) are presented. A compilation of transition frequencies, line intensities, and lower state energies are included for general use in the astronomical community.

Weber, Mark↗

Cryogenic Gellant and Fuel Formulation for Metallized Gelled Propellants: Hydrocarbons and Hydrogen with Aluminum

An experimental program to determine the viability of nanoparticulate gellant materials for gelled hydrocarbons and gelled liquid hydrogen was conducted. The gellants included alkoxides (BTMSE and BTMSH) and silica-based materials. Hexane, ethane, propane and hydrogen were gelled with the newly-formulated materials and their rheological properties were determined: shear stress versus shear rate and their attendant viscosities. Metallized hexane with aluminum particles was also rheologically characterized. The propellant and gellant formulations were selected for the very high surface area and relatively-high energy content of the gellants. These new gellants can therefore improve rocket engine specific impulse over that obtained with traditional cryogenic-fuel gellant materials silicon dioxide, frozen methane, or frozen ethane particles. Significant reductions in the total mass of the gellant were enabled in the fuels. In gelled liquid hydrogen, the total mass of gellant was reduced from 10-40 wt percent of frozen hydrocarbon particles to less that 8 wt percent with the alkoxide.

Wong, Wing↗

Photodissociation of cyanoacetylene: Application to the atmospheric chemistry of Titan

The quantum yield and reaction threshold for the photochemical dissociation of cyanoacetylene into a hydrogen atom and the cyanoethynyl radical have been determined. The quantum yield at 185 nm is approximately 0.09. The threshold is approximately 240 nm. Combination of this data with literature values shows that production of excited-state cyanoacetylene is the major primary process resulting from irradiation between 185 and 254 nm. Also determined are the relative rate constants for the abstraction of a hydrogen atom from hydrogen, methane, and ethane by the cyanoethynyl radical (k(H2):k(CH4):k(C2H6) = 1:9.3:63). Implications of these results for the proposal that hydrogen abstraction plays an important role in the conversion of methane to ethane and in the protection of unsaturated compounds from photoconsumption in the atmosphere of Titan are discussed.

Clarke, David W.↗

Halogen and Sulfur Reactions Relevant to Polar Chemistry

It is widely hypothesized that catalytic cycles involving BrO(x) species play an important role in the episodic destruction of ground-level ozone which is observed in the springtime Arctic boundary layer, although the exact mechanism for production of BrO(x) radicals remains an open question [Barrie et al., Bottenheim et al.; Finlayson-Pitts et al., McConnell et al.] The critical evidence linking ozone depletion with BrO(x) chemistry is an observed negative correlation between ozone and filterable bromine [Bottenheim et al., Kieser et al.] In a recent field study of springtime Arctic boundary layer chemistry [Kieser et al.] ozone concentrations and ethane concentrations were found to be correlated; this observation suggests chlorine atoms (which react rapidly with ethane) may also be an important catalyst for ozone destruction under springtime Arctic conditions.

Wine, Paul H.↗

Use of Less Reactive Materials and More Stable Gases to Reduce Corrosive Wear When Lubricating with Halogenated Gases

The gases CF2Cl-CF2Cl, CF2Cl2, and CF2Br-CF2Br were used to lubricate metals, cermets, and ceramics in this study. One of the criteria for determining the effectiveness of a reactive-gas-lubricated systems is the stability of the halogen-containing gas molecule. The carbon-to-halogen bond in the ethane molecule has extremely good thermal stability superior to the methane analogs (CF2Cl2 and CF2Br2) used in earlier research. For this reason, the ethane compounds CF2Cl-CF2Cl and CF2Br-CF2Br were considered as high-temperature lubricants. Friction and wear studies were made with a hemisphere (3/16-in. rad.) rider sliding in a circumferential path on the flat surface of a rotating disk (21/2-in. diam. ). The specimens of metal alloys, cermets, and ceramics were run In an atmosphere of the various gases with a load of 1200 grams, sliding velocities from 75 to 8000 feet per minute, and temperatures from 75 to 1400 F. The gas CF2Cl-CF2Cl was found to be an effective lubricant for the cermet LT-LB (59.0 Cr, 19.0 Al2O3, 20.0 Mo, 2.0 Ti) and the ceramic Al2O3 sliding on Stellite Star J (cobalt-base alloy) at temperatures to 1400 F. The bromine-containing gas CF2Br-CF2Br was found to give friction and wear values that can be considered to be in a region of effective boundary lubrication for the cermet K175D (nickel-bonded metal carbide) sliding on the metal Hastelloy R-235 (nickel-base alloy) at temperatures to 1200 F.

Buckley, Donald H.↗

Large-scale Distribution of CH4 in the Western North Pacific: Sources and Transport from the Asian Continent

Methane (CH4) mixing ratios in the northern Pacific Basin were sampled from two aircraft during the TRACE-P mission (Transport and Chemical Evolution over the Pacific) from late February through early April 2001 using a tunable diode laser system. Described in more detail by Jacob et al., the mission was designed to characterize Asian outflow to the Pacific, determine its chemical evolution, and assess changes to the atmosphere resulting from the rapid industrialization and increased energy usage on the Asian continent. The high-resolution, high-precision data set of roughly 13,800 CH4 measurements ranged between 1602 ppbv in stratospherically influenced air and 2149 ppbv in highly polluted air. Overall, CH4 mixing ratios were highly correlated with a variety of other trace gases characteristic of a mix of anthropogenic industrial and combustion sources and were strikingly correlated with ethane (C2H6) in particular. Averages with latitude in the near-surface (0-2 km) show that CH4 was elevated well above background levels north of 15 deg N close to the Asian continent. In the central and eastern Pacific, levels of CH4 were lower as continental inputs were mixed horizontally and vertically during transport. Overall, the correlation between CH4 and other hydrocarbons such as ethane (C2H6), ethyne (C2H2), and propane (C3H8) as well as the urban/industrial tracer perchloroethene (C2Cl4), suggests that for CH4 colocated sources such as landfills, wastewater treatment, and fossil fuel use associated with urban areas dominate regional inputs at this time. Comparisons between measurements made during TRACE-P and those of PEM-West B, flown during roughly the same time of year and under a similar meteorological setting 7 years earlier, suggest that although the TRACE-P CH4 observations are higher, the changes are not significantly greater than the increases seen in background air over this time interval.

Bartlett, Karen B.↗

Modification of Jupiter's Stratosphere Three Weeks After the 2009 Impact

Infrared spectroscopy sensitive to thermal emission from Jupiter's stratosphere reveals effects persisting 3 1/2 weeks after the impact of a body in late July 2009. Measurements obtained at 11.7 microns on 2009 August 11 UT at the impact latitude of 56degS (planetocentric), using the Goddard Heterodyne Instrument for Planetary Winds and Composition (HIPWAC) mounted on the NASA Infrared Telescope facility, reveal an interval of reduced thermal continuum emission that extends approx.60deg-80deg towards planetary East of the impact site, estimated to be at 305deg longitude (System III). Retrieved stratospheric ethane mole fraction in the near vicinity of the impact site is enhanced by up to approx.60% relative to quiescent regions at this latitude. Thermal continuum emission at the impact site, and somewhat west of it, is significantly enhanced in the same spectra that retrieve enhanced ethane mole fraction. Assuming that the enhanced continuum brightness near the impact site results from thermalized aerosol debris, then continuum emission by a haze layer can be approximated by an opaque surface inserted at the 45-60 mbar pressure level in the stratosphere in an unperturbed thermal profile, setting a lower limit on the altitude of the top of the ejecta cloud at this time. The reduced continuum brightness east of the impact site can be modeled by an opaque surface near the cold tropopause, consistent with a lower altitude of ejecta/impactor-formed opacity or significantly lesser column density of opaque haze material. The physical extent of the observed region of reduced continuum implies a minimum average velocity of 21 m/s transporting material prograde (East) from the impact. Spectra acquired further East, with quiescent characteristics, imply an average zonal velocity of less than 63 m/s.

Fast, Kelly Elizabeth↗

Detection of Cometary Amines in Samples Returned by the Stardust Spacecraft

The delivery of amino acids to the early Earth by comets and their fragments could have been a significant source of the early Earth's prebiotic organic inventory that led to the emergence of life (Chyba and Sagan, 1992). Over 20 organic molecules including methane, ethane, ammonia, cyanic acid, formaldehyde, formamide, acetaldehyde, acetonitrile, and methanol have been identified by radio spectroscopic observations of the comae of comets Hale-Bopp and Hyakutake (Crovisier et al. 2004). These simple molecules could have provided the organic reservoir to allow the formation of more complex prebiotic organic compounds such as amino acids. After a 7-year mission, the Stardust spacecraft returned to Earth samples from comet Wild 2 on January 15, 2006 providing the opportunity to analyze the organic composition and isotopic distribution of cometary material with state-of-the-art laboratory instrumentation. The Preliminary Examination Team analyses of organics in samples returned by Stardust were largely focused on particles that impacted the collector aerogel and aluminum foil (Sandford et al. 2006). However, it is also possible that Stardust returned a "diffuse" sample of gas-phase organic molecules that struck the aerogel directly or diffused away from the grains after impact. To test this possibility, samples of Stardust flight aerogel and foil were carried through a hot water extraction and acid hydrolysis procedure to see if primary amine compounds were present in excess of those seen in controls. Here we report highly sensitive liquid chromatography time-of-flight mass spectrometry measurements of amino acids and amines in samples returned from a comet (Glavin et al. 2008). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. However, the enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (1 to 2) that are distinct from preflight aerogels (7 to 10), suggest that these amines were captured from Wild 2. It is possible that MA and EA were formed on energetically processed icy grains containing methane, ethane, and ammonia. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of prebiotic organics on the early Earth. To better understand their origin, a systematic compound specific carbon isotopic analysis (C-CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GCQMS/ IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of amino acids extracted from Stardust samples.

Glavin, Daniel P.↗

Detection of Cometary Amines in Samples Returned by the Stardust Spacecraft

The delivery of amino acids to the early Earth by comets and their fragments could have been a significant source of the early Earth's prebiotic organic inventory that led to the emergence of life (Chyba and Sagan, 1992). Over 20 organic molecules including methane, ethane, ammonia, cyanic acid, formaldehyde, formamide, acetaldehyde, acetonitrile, and methanol have been identified by radio spectroscopic observations of the comae of comets Hale-Bopp and Hyakutake (Crovisier et al. 2004). These simple molecules could have provided the organic reservoir to allow the forn1ation of more complex prebiotic organic compounds such as amino acids. After a 7 -year mission, the Stardust spacecraft returned to Earth samples from comet Wild 2 on January 15, 2006 providing the opportunity to analyze the organic composition and isotopic distribution of cometary material with state-of-the-art laboratory instrun1entation. The Preliminary Examination Team analyses of organics in samples returned by Stardust were largely focused on particles that impacted the collector aerogel and aluminum foil (Sandford et al. 2006). However, it is also possible that Stardust returned a "diffuse" sample of gas-phase organic molecules that struck the aerogel directly or diffused away from the grains after impact. To test this possibility, samples of Stardust flight aerogel and foil were carried through a hot water extraction and acid hydrolysis procedure to see if primary amine compounds were present in excess of those seen in controls. Here we report highly sensitive liquid chromatography time-of-flight mass spectron1etry measurements of amino acids and amines in samples returned from a comet (Glavin et al. 2008). A suite of amino acids and amines including glycine, L-alanine, methylamine (MA), and ethylamine (EA) were identified in the Stardust bulk aerogel. With the exception of MA and EA, all other primary amines detected in comet-exposed aerogels were also present in the aerogel witness tile that was not exposed to Wild 2, suggesting that most amines are terrestrial in origin. However, the enhanced abundances of MA, EA, and possibly glycine in comet-exposed aerogel compared to controls, coupled with MA to EA ratios (1 to 2) that are distinct from preflight aerogels (7 to 10), suggest that these amines were captured from Wild 2. It is possible that MA and EA were formed on energetically processed icy grains containing methane, ethane, and ammonia. The presence of cometary amines in Stardust material supports the hypothesis that comets were an important source of pre biotic organics on the early Earth. To better understand their origin, a systematic compound specific carbon isotopic analysis (C-CSIA) via gas chromatography quadrupole mass spectrometry in with parallel with combustion isotope ratio mass spectrometry (GC-QMS/IRMS) is being conducted. We will discuss our latest C-CSIA measurements and what they indicate about the origin of amino acids extracted from Stardust samples.

Glavin, Daniel P.↗

On the Sources of Methane to the Los Angeles Atmosphere

We use historical and new atmospheric trace gas observations to refine the estimated source of methane (CH4) emitted into California's South Coast Air Basin (the larger Los Angeles metropolitan region). Referenced to the California Air Resources Board (CARB) CO emissions inventory, total CH4 emissions are 0.44 +/- 0.15 Tg each year. To investigate the possible contribution of fossil fuel emissions, we use ambient air observations of methane (CH4), ethane (C2H6), and carbon monoxide (CO), together with measured C2H6 to CH4 enhancement ratios in the Los Angeles natural gas supply. The observed atmospheric C2H6 to CH4 ratio during the ARCTAS (2008) and CalNex (2010) aircraft campaigns is similar to the ratio of these gases in the natural gas supplied to the basin during both these campaigns. Thus, at the upper limit (assuming that the only major source of atmospheric C2H6 is fugitive emissions from the natural gas infrastructure) these data are consistent with the attribution of most (0.39 +/- 0.15 Tg yr-1) of the excess CH4 in the basin to uncombusted losses from the natural gas system (approximately 2.5-6% of natural gas delivered to basin customers). However, there are other sources of C2H6 in the region. In particular, emissions of C2H6 (and CH4) from natural gas seeps as well as those associated with petroleum production, both of which are poorly known, will reduce the inferred contribution of the natural gas infrastructure to the total CH4 emissions, potentially significantly. This study highlights both the value and challenges associated with the use of ethane as a tracer for fugitive emissions from the natural gas production and distribution system.

Wennberg, Paul O.↗

Titan as the Abode of Life

Titan is the only world we know other than Earth that has a liquid on its surface. It has a thick atmosphere composed of nitrogen and methane with a thick organic haze. There are lakes, rain, and clouds of methane and ethane. Here, we address the question of carbon-based life living in Titan liquids. Photochemically produced organics, particularly acetylene, in Titan's atmosphere could be a source of biological energy when reacted with atmospheric hydrogen. Light levels on the surface of Titan are more than adequate for photosynthesis but the biochemical limitations due to the few elements available in the environment may lead only to simple ecosystems that only consume atmospheric nutrients. Life on Titan may make use of the trace metals and other inorganic elements produced by meteorites as they ablate in the atmosphere. It is conceivable that H2O molecules on Titan could be used in a biochemistry that is rooted in hydrogen bonds in a way that metals are used in enzymes by life on Earth. Previous theoretical work has shown possible membrane structures in Titan liquids, azotosomes, composed of small organic nitrogen compounds, such as acrylonitrile. The search for a plausible information molecule for life in Titan liquids remains an open research topic - polyethers have been considered and shown to be insoluble at Titan temperatures. Possible search strategies for life on Titan include looking for unusual concentrations of certain molecules reflecting biological selection. Homochirality is a special and powerful example of such biology selection. Environmentally, a depletion of hydrogen in the lower atmosphere may be a sign of metabolism. A discovery of life in liquid methane and ethane would be our first compelling indication that the Universe is full of diverse and wondrous life forms.

H2O molecules on Titan↗