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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Flame Oscillations In Non-Premixed Systems Diffusion Flames and Edge-Flames

Diffusive-thermal instabilities are well known features of premixed and diffusion flames. In one of its form the instability appears as spontaneous oscillations. In premixed systems oscillations are predicted to occur when the effective Lewis number, defined as the ratio of the thermal diffusivity of the mixture to the mass diffusivity of the deficient component, is sufficiently larger than one. Oscillations would therefore occur in mixtures that are deficient in the less mobile reactant, namely in lean hydrocarbon-air or rich hydrogen-air mixtures. The theoretical predictions summarized above are in general agreement with experimental results; see for example [5] where a jet configuration was used and experiments were conducted for various inert-diluted propane and methane flames burning in inert-diluted oxygen. Nitrogen, argon and SF6 were used as inert in order to produce conditions of substantially different Lewis numbers and mixture strength. In accord with the predicted trend, it was found that oscillations arise at near extinction conditions, that for oscillations to occur it suffices that one of the two Lewis numbers be sufficiently large, and that oscillations are more likely to be observed when is relatively large.

Matalon, Moshe↗
NASA NTRS1984

Effect of gravity on halogenated hydrocarbon flame retardant effectiveness

Flammability limits, burning velocities, and minimum ignition energies under initially quiescent conditions were measured for stoichiometric and fuel-lean methane-, ethane-, and propane-air mixtures containing varying concentrations of Halon 1301. The characteristics of near-limit flames were strongly affected by fuel type but not Halon concentration. The conclusions were that the mechanism of the flammability limits was affected by fuel type but not Halon concentration, that the zero-g flammability limit is probably related to a stability criterion which is affected mostly by the molecular diffusion characteristics of the reactant gases and is mostly independent of chemical kinetics, and that the one-g upward flammability and ignition limits provide adequate criteria for safety at one-g and zero-g for both uninhibited and inhibited mixtures.

Ronney, P. D.↗
NASA NTRS1984

Effect of gravity on halogenated hydrocarbon flame retardant effectiveness

Flammability limits, burning velocities, and minimum ignition energies under initially quiescent conditions were measured for stoichiometric and fuel-lean methane-, ethane-, and propane-air mixtures containing varying concentrations of Halon 1301. The characteristics of near-limit flames were strongly affected by fuel type but not Halon concentration. The conclusions were that the mechanism of the flammability limits was affected by fuel type but not Halon concentration, that the zero-g flammability limit is probably related to a stability criterion which is affected mostly by the molecular diffusion characteristics of the reactant gases and is mostly independent of chemical kinetics, and that the one-g upward flammability and ignition limits provide adequate criteria for safety at one-g and zero-g for both uninhibited and inhibited mixtures.

Ronney, P. D.↗
NASA NTRS1999

Influence of Buoyant Convection on the Stability of Enclosed Laminar Flames

An investigation of the stability limits of Enclosed Laminar Flames (ELF) was conducted in the Middeck Glovebox (MGBX) facility on the STS-87 Space Shuttle mission (November to December 1997). The primary objective of the ELF glovebox investigation is to determine the effect of buoyancy on the stability of round, laminar, gas-jet diffusion flames in a co-flow air duct. Comparison tests were conducted in normal gravity to allow isolation and identification of the influence of buoyancy. The results were used to map the lift-off and blow-out stability limits as a function of the fuel and air velocities for the two buoyancy conditions. Approximately 50 tests were conducted during the Space Shuttle mission, using a 50/50 mixture (volume basis) of methane and nitrogen as the fuel. The experimental results verified the hypothesis that substantially greater velocities are required to destabilize the flame in microgravity. The increase in air velocity required to induce lift off in microgravity (compared to normal gravity) was nearly equal to the increase required to induce blow out. Furthermore, the air velocity increase was relatively independent of the fuel flow, except at low fuel flows. At high fuel flows, it was found that the microgravity flames tend to immediately blow out after lift off. This is in agreement with the free-jet theory which suggests that stable lifted flames are not possible for fuels with a Schmidt number of 0.5<Sc<l, such as the diluted methane used in this study. However, stable lifted flames were observed in microgravity at low fuel flows, and in normal gravity, despite the fuel's low Schmidt number. The discrepancy between the experimental data and the theory of Chung and Lee is presumably due to the differences in the flow condition; namely, the ducted flow versus a free jet, and a non-similar velocity profile versus a self-similar profile.

Brooker, John E.↗
DOE OSTI2021

Process for converting alkanes to olefins

A process and apparatus for converting an alkane to an olefin. In one embodiment, the process involves oxidative coupling of an alkane, e.g., methane, with an oxidant, such as air, to produce an olefin having twice the number of carbon atoms as the alkane, e.g., ethylene. In another embodiment, the process involves oxidative dehydrogenation of an alkane, e.g., ethane, with an oxidant to form an olefin having the same number of carbon atoms as the alkane, e.g., ethylene. The process involves passing a flow of the oxidant from a first flow passage through a porous medium; diffusing a flow of the alkane from a second flow passage into the porous medium; and contacting the reactant alkane and the oxidant in the presence of a catalyst within the porous medium to produce the olefin.

Weissman, Jeffrey G.↗
DOE OSTI2022

Process for converting alkanes to olefins

A process and apparatus for converting an alkane to an olefin. In one embodiment, the process involves oxidative coupling of an alkane, e.g., methane, with an oxidant, such as air, to produce an olefin having twice the number of carbon atoms as the alkane, e.g., ethylene. In another embodiment, the process involves oxidative dehydrogenation of an alkane, e.g., ethane, with an oxidant to form an olefin having the same number of carbon atoms as the alkane, e.g., ethylene. The process involves passing a flow of the oxidant from a first flow passage through a porous medium; diffusing a flow of the alkane from a second flow passage into the porous medium; and contacting the reactant alkane and the oxidant in the presence of a catalyst within the porous medium to produce the olefin.

Weissman, Jeffrey↗
DOE OSTI2021

Characterization of shale using Helium and Argon at high pressures

In order to estimate the shale gas in place and the eventual recovery during shale gas operations, one of the key requirements is to accurately characterize the shale’s petrophysical and transport properties such as porosity, permeability, diffusivity, and storage capacity. Despite the many efforts reported in the technical literature aiming to provide an improved understanding of the complex pore structures and the associated fluid flow in gas shales, complete characterization of organic-rich shale samples still poses a big challenge. Here, we have characterized mass transfer and sorption in shale at different length scales using Helium (He) and Argon (Ar) as probe gases. Thermogravimetric analysis (TGA) with a shale cube of ~1 cm 3 in size and gas expansion experiments with a full-diameter core (3.5” in diameter) were used to measure sorption kinetics/isotherms and mass transfer, respectively. Both samples are from the same depth/location in the Marcellus shale formation. The TGA steady-state technique was initially used to generate excess sorption isotherms for Ar, while dynamic TGA experiments were used to study its sorption kinetics. The TGA experiments demonstrate that Ar, which has a similar sorption potential as Methane, but is generally assumed to be inert, adsorbs onto the surfaces of the mesoporous and microporous regions of the shale samples according to a Langmuir-type behavior. Helium expansion experiments, on the full-diameter core, were used to measure the overall porosity, on the basis that He is a non-sorbing and inert gas as compared to Ar. The He expansion experiments, furthermore, allow us to delineate the mass transfer of gas across the inherent hierarchy of pore sizes, including macropores (macro- and microcracks), mesopores and micropores. Similar expansion experiments were also performed with Ar to study the combined impact of mass transfer and sorption. A triple-porosity model (TPM) was utilized to interpret the He expansion experiments with the shale core and to extract (estimate) relevant transport parameters. We report and compare here the diffusivities and permeabilities of the whole core for both He and Ar, as calculated from the modeling and fitting of the experimental data. On the premise that the shale cube is representative of the matrix region of the core, the Ar sorption kinetics from the cube experiments were subsequently combined with the transport parameters extracted from the He experiments to predict the behavior of the Ar expansion test with the full-diameter core. An excellent agreement is observed between the model predictions and the experimental data. The experimental observations and their interpretation indicate that one must be cautious when using Ar to estimate the true porosity and permeability of shales. In addition, we demonstrate that He and Ar probe gases, when used in tandem, can be employed effectively as a tool to characterize shales in terms of mass transfer and sorption dynamics across scales.

04 OIL SHALES AND TAR SANDS↗
NASA NTRS1973

Theoretical model of vertical distributions of CO and CH4 in the mesosphere and upper stratosphere.

Carbon compounds (CO and CO2) and methane are added to an existing computer program (Shimazaki and Laird, 1970, 1972), which calculates diurnal variations in density distributions of pure oxygen compounds, hydrogen compounds, and nitrogen compounds. For the present model calculations, the original program was modified to calculate the steady-state profiles for all constituents, and then these solutions were used as the initial condition for solving the time-dependent equations. The effects of chemical reactions and vertical eddy diffusion transport on the CH4 and CO concentrations above 40 km, where one-dimensional treatment may not be too inappropriate, are discussed. Some of the 15 constituents included in the computer program interact with CO and CH4 chemically, and CH4 is more sensitive to the eddy diffusion coefficient than any other constituent. Therefore it is easier to determine the most appropriate profile of the eddy diffusion coefficient by comparing the model profile with the observations for CH4.

Shimazaki, T.↗
NASA NTRS1992

Methane emissions from tundra environments in the Yukon-Kuskokwin Delta, Alaska

This paper reports CH4 flux to the atmosphere from a variety of tundra environments near Bethel, Alaska during the summer months of 1988. Emissions from wet meadow tundra averaged 144 +/- 31 mg/sq m/d and ranged from 15.6 to 426 mg/sq m/d varying with soil moisture and temperature. Flux from the drier upland tundra was about two orders of magnitude lower and averaged 2.3 +/- 1.1 mg/sq m/d. Tundra lakes emit CH4 from the open water surface as well as from fringing aquatic vegetation; the presence of vegetation significantly enhanced flux over open water rates. Calculated diffusive fluxes from open water varied with lake size, the large lakes emitting 3.8 mg/sq m/d and small lakes emitting an average of 77 mg/sq m/d. An updated estimate of global emissions from tundra indicates an annual fluxes of approximately 11 +/- 3 Tg CH4.

Bartlett, Karen B.↗
DOE OSTI2023

Controlling product selectivity in hybrid gas/liquid reactors using gas conditions, voltage, and temperature

For the conversion of CO 2 into fuels and chemical feedstocks, hybrid gas/liquid-fed electrochemical flow reactors provide advantages in selectivity and production rates over traditional liquid phase reactors. However, fundamental questions remain about how to optimize conditions to produce desired products. Here, using an alkaline electrolyte to suppress hydrogen formation and a gas diffusion electrode catalyst composed of copper nanoparticles on carbon nanospikes, we investigate how hydrocarbon product selectivity in the CO 2 reduction reaction in hybrid reactors depends on three experimentally controllable parameters: (1) supply of dry or humidified CO 2 gas, (2) applied potential, and (3) electrolyte temperature. Changing from dry to humidified CO 2 dramatically alters product selectivity from C 2 products ethanol and acetic acid to ethylene and C 1 products formic acid and methane. Water vapor evidently influences product selectivity of reactions that occur on the gas-facing side of the catalyst by adding a source of protons that alters reaction pathways and intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

This project is part of an ongoing and long-term collaboration among Alexandra Navrotsky (who moved recently from UC Davis to Arizona State University), Nancy Ross at Virginia Tech, and Brian Woodfield at Brigham Young University (BYU) on the thermodynamics and lattice dynamics of nanophase and porous materials. Navrotsky emphasizes energetics of formation and guest molecule sorption by ambient and high temperature calorimetry, Woodfield contributes cryogenic heat capacity measurements, and Ross uses inelastic neutron scattering, X-ray and neutron diffraction, and high pressure studies to probe lattice dynamics and phase transitions. Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. The report below summarizes the work done at UC Davis, which is complemented by work done at BYU (Woodfield) and Virginia Tech (Ross).

36 MATERIALS SCIENCE↗
DOE OSTI2022

The energetics and dynamics of confinement in flexible frameworks and molecular confinement

Porous frameworks form the chemical and structural basis for critical technologies in separations, catalysis, nuclear waste containment and biomedical applications. Hundreds of zeolites and metal organic frameworks (MOFs) have been synthesized, and their ability to separate and store hydrogen, methane and carbon dioxide has been investigated both experimentally and theoretically. Nevertheless, a fundamental and systematic molecular-level understanding of the thermodynamic and structural factors governing the stability and guest-host interactions in these materials lags behind focused studies of specific systems. Because the guest molecules interact with each other and with the host framework, molecular confinement is a finely balanced and complex phenomenon. The ability of the guest molecules to bind and diffuse through the pores is determined by the nature of the host framework which, in turn, responds to the nature and concentration of guest molecules and to pressure and temperature. The work explores how framework flexibility, tailored by structure, composition, temperature and pressure, is a general phenomenon, similar in nature but variable in extent, in both zeolites and MOFs and is part of a free energy landscape in which framework-guest interactions, pressure, and temperature result in changes in framework geometry and, in some cases, phase transitions. These subtle and/or pronounced changes in lattice geometry, energetics, and dynamics can play a decisive role in confinement and in differentiating the binding of molecules of similar size. The free energy landscape created by these structural changes links polymorphism, amorphization, “breathing,” “gate opening” and confinement. Specifically, the generality of such behavior arises from commonalities in lattice dynamics and energetics of frameworks containing a combination of strong rigid bonds and weaker more flexible deformation modes. Identifying and describing these common and collective phenomena is the focus of the research on a selected group of zeolites and MOFs. Structural studies using X-ray and neutron diffraction explore the mechanical functionality of these important materials, specifically how framework materials respond to changes in temperature, pressure and guest loading. These structural studies are combined with calorimetric measurements, using techniques uniquely developed in the participating laboratories, of heats of formation, heat capacities and entropies, and guest-host interactions. The experimental thermodynamic studies are complemented by inelastic neutron scattering studies of the lattice dynamics related both to framework vibrations and to guest-host interactions. This research was a collaboration between UC Davis (A. Navrotsky) BYU (B. Woodfield) and Virginia Tech (N. Ross).

36 MATERIALS SCIENCE↗
NASA NTRS2017

Emulation of Condensed Fuel Flames Using a Burning Rate Emulator (BRE) in Microgravity

The Burning Rate Emulator (BRE) is a gaseous fuel burner developed to emulate the burning of condensed phase fuels. The current study details several tests at the NASA Glenn 5-s drop facility to test the BRE technique in microgravity conditions. The tests are conducted for two burner diameters, 25 mm and 50 mm respectively, with methane and ethylene as the fuels. The ambient pressure, oxygen content and fuel flow rate are additional parameters. The microgravity results exhibit a nominally hemispherical flame with decelerating growth and quasi-steady heat flux after about 5 seconds. The BRE burner was evaluated with a transient analysis to assess the extent of steady-state achieved. The burning rate and flame height recorded at the end of the drop are correlated using two steady-state purely diffusive models. A higher burning rate for the bigger burner as compared to theory indicates the significance of gas radiation. The effect of the ambient pressure and oxygen concentration on the heat of gasification are also examined.

flames↗
DOE OSTI2021

Mechanistic Understanding of Methane Combustion over Ni/CeO 2 : A Combined Experimental and Theoretical Approach

Catalytic oxidation of methane (CH 4 ) over nonprecious Ni/CeO 2 catalysts has received a lot of attention due to the large natural gas reserves found in North America and the prohibitive cost of palladium-based catalysts, commonly used for CH 4 oxidation. However, the catalytic mechanism of CH 4 oxidation over Ni/CeO 2 still remains unclear. Moreover, the parameters affecting the reaction rates, the interaction between nickel and CeO 2 , and the reaction intermediates are still not well understood. In this study, kinetic model fitting, CH 4 temperature-programmed reduction-mass spectroscopy (CH 4 TPR-MS), in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) calculations were combined to elucidate the mechanism of complete oxidation of CH 4 over Ni/CeO 2 . CH 4 TPR-MS showed that the complete oxidation of CH 4 over Ni/CeO 2 requires 55–120 °C lower compared to bare CeO 2 or Ni/quartz sand; complete oxidation of CH 4 took place when the surface oxygen species were abundant, while partial oxidation products (CO, H 2 ) were formed when the oxygen species were depleted. In situ DRIFTS showed that CH 3 , CH 2 , CO, and CO 2 were formed after CH 4 activation over Ni/CeO 2 , while CH 3 O species were not observed. Combining those findings with kinetic model fitting, a redox Mars–van Krevelen (MvK) mechanism showed the best description of the experimental observations. The MvK mechanism involves the reaction of dissociated oxygen species with gas-phase CH 4 while water inhibits the reaction rate by adsorbing on the oxidized sites. Moreover, CH 4 activation leads to the reduction of the active sites and oxygen vacancy formation followed by reoxidation of the active sites by gas-phase O 2 . A CH 4 oxidation reaction pathway over Ni/CeO 2 is proposed by DFT calculations. In summary, the findings shown here suggest that CH 4 oxidation over Ni/CeO 2 follows a redox MvK mechanism and provides guidance for the rational design of non-precious-metal catalysts for CH 4 oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2009

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.↗
NASA NTRS2010

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.↗
DOE OSTI2020

Coupled confined phase behavior and transport of methane in slit nanopores

The proximity of the order of magnitude molecular mean free path and pore sizes in nanopores leads to remarkable interactions between molecules and walls. In such systems, the thermodynamic property and the transport behavior of fluids deviate from those at bulk conditions. Molecular dynamics (MD) simulation may be used to investigate the effects of confinement on fluid physics in nanosize pores. However, translating these subscale observations into a larger scale of interest remains a challenging task. In this work, we propose a modified extension of Peng-Robinson equation of state (PR-EOS) motivated and guided by MD simulation results. The shift of critical properties, i.e., pressure and temperature, are evaluated independently. A temperature dependent parameter is introduced to account for the existence of capillary pressure in the two-phase region. Here, this formulation is capable of capturing the shift in critical properties as well as density phase diagrams under various confinement scenarios. We incorporate the proposed EOS in the lattice Boltzmann method (LBM) to study coupled confined phase behavior and transport of methane in nano-size slit pores. Adsorptive strength is determined such that the resulting density ratio matches that from MD simulation. Results indicate that the use of the proposed EOS leads to smaller fluid velocities compared to PR-EOS. This effect is due to stronger interactions between fluid particles under confinement. Also, results show that transport characteristics are impacted by the pressure of the system: in systems with a relatively low pressure, transport seems to be dominated by Knudsen diffusion; however, at a higher pressure, the contribution from viscous flow increases as the pore widens while the influence of Knudsen and surface diffusion diminishes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗