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At least 433 records · Page 24

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DOE OSTI2024

Determination of the Diffusion Coefficients of Binary CH4 and C2H6 in a Supercritical CO2 Environment (500–2000 K and 100–1000 atm) by Molecular Dynamics Simulations

The self-diffusion coefficients of carbonaceous fuels in a supercritical CO2 environment provide transport information that can help us understand the Allam Cycle mechanism at a high pressure of 300 atm. The diffusion coefficients of pure CO2 and binary CO2/CH4 and CO2/C2H6 at high temperatures (500 K~2000 K) and high pressures (100 atm~1000 atm) are determined by molecular dynamics simulations in this study. Increasing the temperature leads to an increase in the diffusion coefficient, and increasing the pressure leads to a decrease in the diffusion coefficients for both methane and ethane. The diffusion coefficient of methane at 300 atm is approximately 0.012 cm2/s at 1000 K and 0.032 cm2/s at 1500 K. The diffusion coefficient of ethane at 300 atm is approximately 0.016 cm2/s at 1000 K and 0.045 cm2/s at 1500 K. The understanding of diffusion coefficients potentially leads to the reduction in fuel consumption and minimization of greenhouse gas emissions in the Allam Cycle.

Energy & Fuels↗

DOE OSTI2017

Implications for Extraterrestrial Hydrocarbon Chemistry: Analysis of Ethylene (C{sub 2}H{sub 4}) and D4-Ethylene (C{sub 2}D{sub 4}) Ices Exposed to Ionizing Radiation via Combined Infrared Spectroscopy and Reflectron Time-of-flight Mass Spectrometry

The processing of the hydrocarbon ice, ethylene (C{sub 2}H{sub 4}/C{sub 2}D{sub 4}), via energetic electrons, thus simulating the processes in the track of galactic cosmic-ray particles, was carried out in an ultrahigh vacuum apparatus. The chemical evolution of the ices was monitored online and in situ utilizing Fourier transform infrared spectroscopy (FTIR) and during temperature programmed desorption, via a quadrupole mass spectrometer utilizing electron impact ionization (EI-QMS) and a reflectron time-of-flight mass spectrometer utilizing a photoionization source (PI-ReTOF-MS). Several previous in situ studies of ethylene ice irradiation using FTIR were substantiated with the detection of six products: [CH{sub 4} (CD{sub 4})], acetylene [C{sub 2}H{sub 2} (C{sub 2}D{sub 2})], the ethyl radical [C{sub 2}H{sub 5} (C{sub 2}D{sub 5})], ethane [C{sub 2}H{sub 6} (C{sub 2}D{sub 6})], 1-butene [C{sub 4}H{sub 8} (C{sub 4}D{sub 8})], and n -butane [C{sub 4}H{sub 10} (C{sub 4}D{sub 10})]. Contrary to previous gas phase studies, the PI-ReTOF-MS detected several groups of hydrocarbon with varying degrees of saturation: C{sub n}H{sub 2n+2} (n = 4–10), C{sub n}H{sub 2n} ( n = 2–12, 14, 16), C{sub n}H{sub 2n−2} ( n = 3–12, 14, 16), C{sub n}H{sub 2n−4} (n = 4–12, 14, 16), C{sub n}H{sub 2n−6} (n = 4–10, 12), C{sub n}H{sub 2n−8} ( n = 6–10), and C{sub n}H{sub 2n−10} ( n = 6–10). Multiple laboratory studies have shown the facile production of ethylene from methane, which is a known ice constituent in the interstellar medium. Various astrophysically interesting molecules can be associated with the groups detected here, such as allene/methylacetylene (C{sub 3}H{sub 4}) or 1, 3-butadiene (C{sub 4}H{sub 6}) and its isomers, which have been shown to lead to polycyclic aromatic hydrocarbons. Finally, several hydrocarbon groups detected here are unique to ethylene ice versus ethane ice and may provide understanding of how complex hydrocarbons form in astrophysical environments.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1973

Friction-induced surface activity of some hydrocarbons with clean and oxide-covered iron

Sliding friction studies were conducted on a clean and oxide-covered iron surface with exposure of that surface to various hydrocarbons. The hydrocarbons included ethane, ethylene ethyl chloride, methyl chloride, and vinyl chloride. Auger cylindrical mirror analysis was used to follow interactions of the hydrocarbon with the iron surface. Results with vinyl chloride indicate friction induced surface reactivity, adsorption to surface oxides, friction sensitivity to concentration and polymerization. Variation in the loads employed influence adsorption and accordingly friction. In contrast with ethyl and vinyl chloride, friction induced surface reactivity was not observed with ethane and ethylene.

Buckley, D. H.↗

NASA NTRS1973

Friction induced surface activity of some simple organic chlorides and hydrocarbons with iron.

Sliding friction studies were conducted on an iron surface with exposure of that surface to various hydrocarbons and organic chlorides. The hydrocarbons included ethane, ethylene, ethyl chloride, methyl chloride and vinyl chloride. Auger cylindrical-mirror analysis was used to follow interactions of the hydrocarbon and organic chlorides with the iron surface. Results with vinyl chloride indicate friction-induced surface reactivity, adsorption to surface oxides, friction sensitivity to concentration and polymerization. Variation in the loads employed influence adsorption and, accordingly, friction. Unlike results with ethyl and vinyl chloride, friction-induced surface reactivity was not observed with ethane and ethylene.

Buckley, D. H.↗

NASA NTRS1974

Parametric performance of extruded axial grooved heat pipes from 100 to 300 K

Extensive performance data derived from tests with an aluminum axial grooved extruded heat pipe is presented for oxygen, methane, ethane, and ammonia as working fluids. The effects of operating temperature, fluid inventory, heat flux, and elevation on the transport capability and the evaporator and condenser film coefficients are measured and compared to theory. The data correlation indicates that, in addition to the viscous pressure drop of the fluid, a vapor induced liquid pressure drop must be taken into account at temperatures near or below the normal boiling point of the fluid. Methane, ethane, and ammonia are all suitable working fluids for this groove geometry; however, oxygen, because of its low static height, is at best marginal in the 100-120 K range.

Schlitt, K. R.↗

NASA NTRS1982

Evaluation of dopants in hydrogen to reduce hydrogen permeation in candidate Stirling engine heater head tube alloys at 760 deg and 820 deg

Alloy tubes filled with hydrogen doped with various amounts of carbon monoxide, carbon dioxide, ethane, ethylene, methane, ammonia, or water were heated in a diesel fuel-fired Stirling engine simulator materials test rig for 100 hours at 21 MPa and 760 or 820 C to determine the effectiveness of the dopants in reducing hydrogen permeation through the hot tube walls. Ultra high purity (UHP) hydrogen was used for comparison. The tube alloys were N-155, A-286, Incoloy 800, Nitronic 40, 19-9DL, 316 stainless steel, Inconel 718, and HS-188. Carbon dioxide and carbon monoxide in the concentration range 0.2 to 5 vol % were most effective in reducing hydrogen permeation through the hot tube walls for all alloys. Ethane, ethylene, methane, ammonia, and water at the concentrations investigated were not effective in reducing the permeation below that achieved with UHP hydrogen. One series of tests were conducted with UHP hydrogen in carburized tubes. Carburization of the tubes prior to exposure reduced permeation to values similar to those for carbon monoxide; however, carbon dioxide was the most effective dopant.

Misencik, J. A.↗

NASA NTRS1983

Photolysis of methane and the ionosphere of Uranus

Photochemical calculations for Uranus predict an extensive region of condensation of acetylene, ethane and methane in the vicinity of the temperature inversion layer. This could explain why ethane was not detected on Uranus, unlike Neptune which has a much warmer inversion layer. Subsequent snow-out of the condensibles is expected to result in reduced visibility in the troposphere. Ionospheric calculations for the equatorial region to be probed by Voyager, indicate peak electron concentrations on the order of 5,000 per cu cm, if dynamical effects are important. Upper limit to the electron peak is 30,000 per cu cm. Exospheric temperatures as high as 200-250K are conceivable.

Atreya, S. K.↗

NASA NTRS1983

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.↗

NASA NTRS1984

Development and evaluation of a plasma jet flameholder for scramjets

The objective of the work reported herein was to explore the use of a continuous operation plasma torch as an ignitor and flameholder for scramjet combustion. This research was motivated by the desire to eliminate the use of pyrophoric or toxic ignition and/or combustion enhancement materials in operational aircraft or shipboard systems. The total temperatures and torch powers used to ignite/flamehold Mach 2 combustion with hydrogen, ethylene, ethane, and methane were determined. The minimum ignition total temperatures for the fuels tested were hydrogen - 1065 R (lowest test temperature); ethylene - 1500 R; ethane - 2000 R; methane - 2700 R. These temperatures were obtained while operating the torch at a nominal 2 kw net power. The torch was shown to be a good ignitor and flameholder in that both hydrogen and hydrocarbon fuels could be stabilized by the torch and would 'blow off' when the torch was extinguished. The effectiveness of the torch was very sensitive to relative fuel injection location. Best combustion resulted when fuel was injected both upstream and downstream of the torch. These results indicated that an adiabatic plasma torch operating at about 2 kw could be an effective ignitor and flameholder for high-speed combustion.

Northam, G. B.↗

NASA NTRS1986

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% 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, A. L.↗

NASA NTRS1986

Advanced infrared astronomy

The CO2 laser heterodyne spectrometer was used at the 3-m IRTF on Mauna Kea to make measurements of Mars during the 1984 opposition. Analysis of the observations of the mesospheric non-thermal emission demonstrated the existence of a warming of the Mars polar mesosphere, similar to the seasonal effects which are well known to occur at the Earth's mesopause. A search for CO2 and NH3 on Comet Halley was done with the new Kitt Peak system as well as with the IRTF heterodyne system. A Lamb-dip absorption cell was designed and constructed. Its use will allow extreme frequency stabilization of the laser local oscillator, which will greatly facilitate measurements of winds and dynamical phenomena. The Lamb-dip cell was used at Kitt Peak to study zonal and meridional winds in the atmosphere of Venus. Water vapor was detected in Comet Halley using Fourier transform spectrometer. The 2.65 micrometer upsilon sub 3 band was seen in emission, confirming non-thermal-equilibrium excitation models for comets. A study was made of the variability of Jovian ethane emission. The average volume mixing ratio of ethane in the Jovian stratosphere was found to be 3x10 to the -6 power, with the greatest variability seen in the auroral regions.

Mumma, M. J.↗

NASA NTRS1987

Measurement of methane and other light hydrocarbons in the troposphere and lower stratosphere

The volume mixing ratios of methane, acetylene, ethane, and propane were measured in the troposphere and stratosphere on April 5, 1984, at 33 deg N, over New Mexico, using the technique of grab sampling by evacuated spheres on a balloon platform. Tropospheric volume mixing ratios were CH4, 1.59 ppm; C2H2, 358 ppt (parts per trillion); C2H6, 365 ppt; and C3H8, 1440 ppt. In the stratosphere, acetylene was 60 ppt. For ethane and propane the mixing ratios at 11.6 km were 441 ppt and 84 ppt, respectively.

Aikin, A. C.↗

NASA NTRS1987

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.↗

NASA NTRS1989

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.↗

NASA NTRS1990

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.↗

NASA NTRS1990

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.↗

NASA NTRS1991

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↗

NASA NTRS1992

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.↗