Engineering topics

Khare, B. N.

Publications and source records attributed to Khare, B. N..

At least 19 records

NASA NTRS2005

Experimental Study on Interactions Between H Atoms and Organic Haze

In Titan s atmosphere composed of N2 and CH4, irradiations of both solar ultraviolet light and charged particles induce active chemical reactions. In the processes of these reactions, a large amount of hydrogen (H) atoms are expected to be formed by dissociation of CH4 and other hydrocarbons [e.g., 1, 2]. Theoretical models suggest that these active H atoms need to be converted to stable hydrogen molecules (H2) efficiently to maintain unsaturated hydrocarbons and organic haze in Titan s atmosphere [e.g., 1]. Furthermore, molecular hydrogen is an important greenhouse effect gas in Titan s atmosphere, and small variation in its abundance strongly affects Titan s surface temperature [3]. Thus, the formation of H2 molecules from H atoms is a key reaction for both the atmospheric chemistry and the surface environment of Titan. Although several numerical calculations have been conducted to investigate the atmospheric chemistry of Titan with hypothesized recombination reactions of H atoms, such as catalytic scheme of C4H2 [e.g., 1, 2], it is still unclear what chemical reaction is responsible for the conversion of H atoms to H2 molecules in Titan s atmosphere.

Sekine, Y.↗

NASA NTRS2003

Spectral Characteristic of Tholin Produced from Possible Early Earth Atmospheres and its Role in Antigreenhouse Effect on Early Earth

We have produced organic material simulating a methane photochemical haze in a CO2- rich atmosphere of the early Earth by irradiating gas mixtures in an inductively coupled cold plasma chamber with pressure approx. 0.25 mbar at 100 W total power. The flow rate was 24 cm3 min. We added progressively higher levels of CH, by combining gas mixtures of N2/CH4 (9/1) and N2/CO2 (9/1) to change the ratio of CH4/CO2. Tholin was accumulated for 5 hours in each experiment; the onset of tholin formation is in the range CH4/CO2 = 0.5 to 1. As the mixing ratio of CH, is increased, the production rate of the brownish tholin film increases. IR spectra showed the C-H and N-H bands similar to that of Titan tholin and closely resemble Titan tholin made at 0.13 mbar pressure. A decrease in the CH bonds on decreasing CH4/CO2 is noted. Ether bands (-(2-O-C) were tentatively detected, but no detectable carbonyl (C=O) band was found. The absorption in the UV region for the early Earth tholin is found to be substantially greater than the Titan tholin. Quantitative values of the optical constants of early Earth tholin are currently being measured.

Khare, B. N.↗

NASA NTRS2002

Organic Solid Matter as a Coloring Agent in Outer Solar System Bodies

Small bodies in the outer Solar System OSS, exhibit a range of color, or slope of the reflectance in the photovisual spectral region, ranging from neutral to very red, sometimes with and sometimes without distinct absorption bands. These objects range in geometric albedo from 0.03 to 1.0, with the higher albedo objects typically showing clear evidence of water ice. Water ice has also been found in a few objects with albedo 0. 1 or less. We explore here the identification of the material or materials that color these icy and non-icy surfaces through scattering models that incorporate minerals, meteoritic material, and organic solids (tholins) produced ID the laboratory by energy deposition in ices and gases. These models must match not only the color in the photovisual region, but the spectral reflectance properties throughout the near-infrared. Among some classes of objects, such as Kuiper Belt objects, the coloring agent may be a single material that is present in greater or lesser abundance, thus accounting for the range in color from neutral to very red. This may also apply to the Centaur objects, the Jovian Trojans, and the outer-main belt asteroids, each taken as a separate class. If so, each class may be colored to varying degrees by a different material, or they all might be colored by a common material that is widespread throughout the OSS, from 3 to 50 AU, and beyond. In this paper, we model the reflectances of "Kuiper Belt objects, Centaurs, Trojans, outer ARAB asteroids, and planetary satellites. Our models show that the reddest surfaces cannot be colored by minerals or meteoritic materials, but can be matched throughout the photovisual and near-infrared by organic solids, specifically certain tholins.

Cruikshank, D. P.↗

NASA NTRS1997

Measurement of Optical Properties of Small Particles

We have measured the optical constants of montmorillonite and the separated coats and cores of B. subtilis spores over the wavelength interval from 200 nm to 2500 nm. The optical constants of kaolin were obtained over the wavelength interval from 130 nm to 2500 nm. Our results are applicable to the development of systems for detection of airborne biological contaminants. Future work will include measurement of the optical constants of B. cereus spores, B. sub tilts vegetative cells, egg albumin, illite, and a mixture (by weight) of one third kaolin, one third montmorillonite, and one third illite.

Arakawa, E. T.↗

NASA NTRS1994

Optical properties of poly-HCN and their astronomical applications

Matthews (1992) has proposed that HCN "polymer" is ubiquitous in the solar system. We apply vacuum deposition and spectroscopic techniques previously used on synthetic organic heteropolymers (tholins), kerogens, and meteoritic organic residues to the measurement of the optical constants of poly-HCN in the wavelength range 0.05-40 micrometers. These measurements allow quantitative comparison with spectrophotometry of organic-rich bodies in the outer solar system. In a specific test of Matthews' hypothesis, poly-HCN fails to match the optical constants of the haze of the Saturnian moon, Titan, in the visible and near-infrared derived from astronomical observations and standard models of the Titan atmosphere. In contrast, a tholin produced from a simulated Titan atmosphere matches within the probable errors. Poly-HCN is much more N-rich than Titan tholin.

Optics↗

NASA NTRS1993

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

PAHs are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites, are identified, with a net abundance of about 0.0001 g/g (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins.

Sagan, Carl↗

NASA NTRS1993

Production and optical constraints of ice tholin from charged particle irradiation of (1:6) C2H6/H2O at 77 K

Fifty separate irradiations of a 6:1 mixture of H2O/C2H6 ice conducted over a 5-month period have yielded sufficient tholin for the determination of its physical constants in the 0.06 to 40 micron range. While the imaginary part of the refractive index k was obtained by transmission measurements on thin-film samples and Kramers-Kronig analysis (KKA), the real part of the refractive index was obtained by KKA and ellipsometry; these data may prove useful in cometary and outer solar system spectrometric interpretation.

Khare, B. N.↗

NASA NTRS1992

Titan: a laboratory for prebiological organic chemistry

When we examine the atmospheres of the Jovian planets (Jupiter, Saturn, Uranus, and Neptune), the satellites in the outer solar system, comets, and even--through microwave and infrared spectroscopy--the cold dilute gas and grains between the stars, we find a rich organic chemistry, presumably abiological, not only in most of the solar system but throughout the Milky Way galaxy. In part because the composition and surface pressure of the Earth's atmosphere 4 x 10(9) years ago are unknown, laboratory experiments on prebiological organic chemistry are at best suggestive; but we can test our understanding by looking more closely at the observed extraterrestrial organic chemistry. The present Account is restricted to atmospheric organic chemistry, primarily on the large moon of Saturn. Titan is a test of our understanding of the organic chemistry of planetary atmospheres. Its atmospheric bulk composition (N2/CH4) is intermediate between the highly reducing (H2/He/CH4/NH3/H2O) atmospheres of the Jovian planets and the more oxidized (N2/CO2/H2O) atmospheres of the terrestrial planets Mars and Venus. It has long been recognized that Titan's organic chemistry may have some relevance to the events that led to the origin of life on Earth. But with Titan surface temperatures approximately equal to 94 K and pressures approximately equal to 1.6 bar, the oceans of the early Earth have no ready analogue on Titan. Nevertheless, tectonic events in the water ice-rich interior or impact melting and slow re-freezing may lead to an episodic availability of liquid water. Indeed, the latter process is the equivalent of a approximately 10(3)-year-duration shallow aqueous sea over the entire surface of Titan.

Non-NASA Center↗

NASA NTRS1991

Organic synthesis in the outer Solar System: Recent laboratory simulations for Titan, the Jovian planets, Triton and comets

We tabulate the most abundant gases and their radiation yields, for two experimental pressures: 0.24 mb, more relevant to upper atmosphere excitation, and 17 mb, more relevant to tropospheric, cosmic ray excitation. The yields computed in the 0.24 mb experiment combined with measured electronic fluxes and a simple, eddy diffusion model of Titan's atmosphere predict abundances of detected molecules in agreement with those found by Voyager and for heavier products, in somewhat better agreement with observation than photochemical absolute reaction rate kinetics models. All Voyager organics are accounted for and no detectable products are found that Voyager did not detect. A striking increase of products with multiple bonds is found with decreasing pressure. Hydrocarbon abundances decline slowly with increasing carbon number. Additionally, we list preliminary estimates for the yield of the heteropolymer, which seems to be produced in a quantity comparable (in moles of C+N consumed) to the total amount of gaseous product. The production rate required to sustain Titan's haze against sedimentation also indicates yields of this order. As can be seen from the table, over 10(exp 9) years substantial amounts of these products can accumulate on the surface -- ranging from cm thickness for the (C+N equals 4) species to a meter or more for HCN and C2H2; we also expect a meter or more of tholins. Similar analyses have been or are being done for the Jovian planets and Triton. Charged particle irradiation of hydrocarbon clathrates or mixed hydrocarbon/water ices produces a range of organic products, reddening and darkening of the ices and characteristic infrared spectra. From such spectra, the predicted emission by fine particles in cometary comae well-matches the observed 3.4 micron emission spectra of Comet Halley and other recent comets. Heliocentric evolution of organic emission features in comets is predicted. Organic products of such ice irradiation may account for colors and albedos on some of the satellites in the outer solar system, especially Triton and Pluto, where solid methane is known to exist.

Sagan, C.↗

NASA NTRS1991

Studies of volatiles and organic materials in early terrestrial and present-day outer solar system environments

A review and partial summary of projects within several areas of research generally involving the origin, distribution, chemistry, and spectral/dielectric properties of volatiles and organic materials in the outer solar system and early terrestrial environments are presented. The major topics covered include: (1) impact delivery of volatiles and organic compounds to the early terrestrial planets; (2) optical constants measurements; (3) spectral classification, chemical processes, and distribution of materials; and (4) radar properties of ice, hydrocarbons, and organic heteropolymers.

Sagan, Carl↗

NASA NTRS1991

Plasma discharge in N2 + CH4 at low pressures - Experimental results and applications to Titan

Results are reported from laboratory continuous-flow plasma-discharge experiments designed to simulate the formation of hydrocarbons and nitriles from N2 and CH4 in the atmosphere of Titan. Gas-chromatography and mass-spectrometry data were obtained in experiments lasting up to 100 h at temperature 295 K and pressure 17 or 0.24 mbar, modeling (1) cosmic-ray-induced processes in the Titan troposphere and (2) processes related to stratospheric aurorae excited by energetic electrons and ions from the Saturn magnetosphere, respectively. The results are presented in extensive tables and graphs, and the 0.24-mbar yields are incorporated into an eddy-mixing model to give stratospheric column abundances and mole fractions in good agreement with Voyager IRIS observations.

Thompson, W. Reid↗

NASA NTRS1990

Microbial metabolism of Tholin

Tholin, a class of complex organic heteropolymers hypothesized to possess wide solar system distribution, is shown to furnish the carbon and energy requirements of a wide variety of common soil bacteria which encompasses aerobic, anaerobic, and facultatively anaerobic bacteria. Some of these bacteria are able to derive not merely their carbon but also their nitrogen requirements from tholin. The palatability of tholins to modern microbes is speculated to have implications for the early evolution of microbial life on earth; tholins may have formed the base of the food chain for an early heterotrophic biosphere, prior to the evolution of autotrophy on the early earth.

Stoker, C. R.↗

NASA NTRS1989

Triton - Stratospheric molecules and organic sediments

Continuous-flow plasma discharge techniques show production rates of hydrocarbons and nitriles in N2 + CH4 atmospheres appropriate to the stratosphere of Titan, and indicate that a simple eddy diffusion model together with the observed electron flux quantitatively matches the Voyager IRIS observations for all the hydrocarbons, except for the simplest ones. Charged particle chemistry is very important in Triton's stratosphere. In the more CH4-rich case of Titan, many hydrocarbons and nitriles are produced in high yield. If N2 is present, the CH4 fraction is low, but hydrocarbons and nitriles are produced in fair yield, abundances of HCN and C2H2 in Triton's stratosphere exceed 10 to the 19th molecules/sq cm per sec, and NCCN, C3H4, and other species are predicted to be present. These molecules may be detected by IRIS if the stratosphere is as warm as expected. Both organic haze and condensed gases will provide a substantial UV and visible opacity in Triton's atmosphere.

Thompson, W. Reid↗

NASA NTRS1989

Solid organic residues produced by irradiation of hydrocarbon-containing H2O and H2O/NH3 ices - Infrared spectroscopy and astronomical implications

Plasma-discharge irradiations were conducted for the methane clathrate expected in outer solar system satellites and cometary nuclei; also irradiated were ices prepared from other combinations of H2O with CH4, C2H6, or C2H2. Upon evaporation of the yellowish-to-tan irradiated ices, it is found that a colored solid film adheres to the walls of the reaction vessel at room temperature. These organic films are found to exhibit IR band identifiable with alkane, aldehide, alcohol, and perhaps alkene, as well as substituted aromatic functional groups. These spectra are compared with previous studies of UV- or photon-irradiated nonclathrated hydrocarbon-containing ices.

Khare, B. N.↗

NASA NTRS1989

Organic solids produced from simple C/H/O/N ices by charged particles - Applications to the outer solar system

The effects of charged particle irradiation by cold plasma discharge on surfaces of H2O:CH4 clathrate with a 200:1 ratio and on ices composed of H2O and C2H6 or C2H2 are examined. The molecules studies are found in Comet Halley and are plausible constituents in icy outer solar system objects. The IR transmission spectra of four ice-tholin residues obtained in the laboratory are compared with spectra produced by irradiation of gases and ices containing simple hydrocarbons. The similarities between CH4 clathrate residue and Halley organic grains, and the surface transport or atmospheric replenishment activity on Triton and Pluto are discussed.

Khare, B. N.↗

NASA NTRS1987

Coloration and darkening of methane clathrate and other ices by charged particle irradiation - Applications to the outer solar system

The results of laboratory experiments simulating the irradiation of hydrocarbon-H2O or hydrocarbon-H2O/NH3 clathrates by charged particles in the outer solar system are reported. Ices produced by condensing and boiling liquid CH4 on an H2O frost surface at 100 K or by cocondensing frosts from gaseous mixtures were exposed to coronal-discharge electron irradiation at 77 K, and the spectral properties of the irradiated surfaces were determined. Significant darkening of the initially white ices was observed at doses of 1 Gerg/sq cm, corresponding to 8-500 yrs of irradiation by Uranian magnetospheric electrons on the surfaces of the principal Uranian satellites, or to total destruction of CH4 in the upper 1 mm of the satellite surfaces after 0.05-3.0 Myr. It is estimated that 10 m or more of icy satellite or comet surfaces would be radiation-hardened to a CH4-free ice-tholin mixture over 4 Gyr.

Thompson, W. Reid↗

NASA NTRS1987

Solid hydrocarbon aerosols produced in simulated Uranian and Neptunian stratospheres

Solid hydrocarbon films were deposited in an RF plasma discharge of various CH4/H2/He mixtures under conditions simulating the formation of solid aerosols by magnetospheric charged particles in the stratospheres of Uranus and Neptune. The percentage of CH4 ranged from 0.0002 to 100 percent; the pressure in the discharge chamber was either 130 or 660 microbar; and the films produced were yellow to deep red-brown in color and 2-25 microns thick. The real and imaginary parts of the refractive index at wavelengths from 350 nm to 2.5 microns were determined for all the films, and the results are compared with observational data and the predictions of theoretical models in extensive tables and graphs. Good agreement is demonstrated, suggesting that aerosol production by this mechanism may be competitive with UV or charged-particle irradiation of hydrocarbon condensates.

Khare, B. N.↗

NASA NTRS1987

Light hydrocarbons from plasma discharge in H2-He-CH4 - First results and Uranian auroral chemistry

The production of light hydrocarbons by precipitating magnetospheric electrons in the Uranian stratosphere is simulated in laboratory experiments. The products of continuous-flow glow discharges of H2-He-CH4 mixtures containing 0.0012 or 0.022 mol pct CH4 at pressures 0.63-57 mbar are trapped at 77 K, measured manometrically, and identified by gas chromatography and mass spectroscopy; the results are presented in tables and characterized in detail. The globally averaged rate for the production of higher hydrocarbons by this mechanism on Uranus is estimated as 3 x 10 to the 6th C/sq cm sec and shown to be similar to that for photochemical production, while the local rate for the auroral zones is significantly higher than the corresponding photochemical rate. A decrease in yield with increasing molecular complexity is also noted.

Thompson, W. Reid↗