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At least 1,369 records · Page 76
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Mass spectrometric studies of trimethylindium pyrolysis

The kinetics of the pyrolysis of trimethylindium (TMIn) in He, D2, and H2 carriers was investigated using the atmospheric pressure flow-tube apparatus described by Larsen et al. (1987) and a time-of-flight mass spectrometer. The rate constant for the pyrolysis of TMIn in He was found to be comparable to that found by Jacko and Price (1964) for TMIn in toluene carrier (a radical scavenger), indicating that TMIn decomposes in He not by radical attack of methyl groups, but by homolytic fission. The decomposition of TMIn is enhanced in D2 and H2 carriers, where the principal products are CH3D and C2H6, and CH4 and C2H6, respectively, indicating that the reaction pathway in these carriers is different from those in He and toluene. The pyrolysis in H2 and D2 is attributed to a radical attack by H or D on TMIn. A reaction mechanism involving a short-lived hypervalent DTMIn species was proposed and was tested using numerical modeling techniques.

Buchan, N. I.↗
NASA NTRS1988

A mass spectrometric study of the simultaneous reaction mechanism of TMIn and PH3 to grow InP

The reaction mechanisms for the growth of InP from various mixtures of trimethyl indium (TMIn) and PH3 by OMVPE were investigated using mass spectrometry and a D2 ambient for isotopic labeling of the reaction products. It was found that, whereas TMIn alone pyrolyzes homogeneously, forming CH3D, and PH3 alone pyrolyzes heterogeneously, producing H2, the pyrolysis reactions of TMIn and PH3 together are completely different. The pyrolysis temperatures of both TMIn and PH3 are reduced (by 50 C for TMIn and 225 C for PH3), and the sole product is CH4 at high values of the PH3/TMIn ratio. The pyrolysis reaction is shown to be coupled (as evidenced by the equal depletion of TMIn and PH3 from the vapor) and, at temperatures below 400 C, heterogeneous.

Buchan, N. I.↗
NASA NTRS1989

Laboratory experiments on carbonaceous material as a source for the red rectangle visual emissions

The authors subjected mixtures of CO, Ar, N2, H2O, and CH4 with 42 percent and 8 percent argon to an electrical discharge, froze out the reaction products at T about 20 K, and subsequently warmed the sample to room temperature. This resulted in a stable residue having broad-band fluorescence. It is suggested tht interstellar grains in the Red Rectangle/HD 44179 are coated with a residue of generally similar composition that is responsible for the broad emission feature in the 5400-7500 A spectral region.

Wdowiak, Thomas J.↗
NASA NTRS1989

Time-resolved simplified chemical kinetics modelling using computational singular perturbation

A CO-CH4-air reaction system is used to demonstrate the computational singular perturbation (CSP) method for deriving time-resolved simplified chemical kinetics models. CSP provides a programmable algorithm to group the given collection of elementary reactions into reaction groups which are ordered according to their speed. The concept of Importance Index k(m)exp s is introduced: k(m)exp s is defined to be a number between 0 and 1 which measures the importance of the m-th reaction group to the s-th reactant and can readily be computed from data generated by CSP. It is suggested that the robustness of the solutions of the reaction system can be qualitatively assessed by inspecting the Importance Index data.

Lam, S. H.↗
NASA NTRS1989

Surface studies relevant to silicon carbide chemical vapor deposition

Reactions of C2H4, C3H8, and CH4 on the Si(111) surface and C2H4 on the Si(100) surface were investigated for surface temperatures in the range of 1062-1495 K. Results led to the identification of the reaction products, a characterization of the solid-state transport process, a determination of the nucleation mechanism and growth kinetics, and an assessment of orientation effects. Based on these results and on the modeling studies of Stinespring and Wormhoudt (1988) on the associated gas phase chemistry, a physical model for the two-step beta-SiC CVD process is proposed.

Stinespring, C. D.↗
NASA NTRS1989

Trace gas emissions from chaparral and boreal forest fires

Using smoke samples collected during low-level helicopter flights, the mixing ratios of CO2, CO, CH4, total nonmethane hydrocarbons, H2, and N2O over burning chaparral in southern California and over a burning boreal forest site in northern Ontario, Canada, were determined. Carbon dioxide-normalized emission ratios were determined for each trace gas for conditions of flaming, mixed, and smoldering combustion. The emission ratios for these trace gases were found to be highest for the smoldering combustion, generally thought to be the least efficient combustion stage. However, high emission ratios for these gases could be also produced during very vigorous flaming combustion.

Cofer, Wesley R., III↗
NASA NTRS1989

Measurements of collision-broadened line widths in the nu4-fundamental band of (C-12)H4 at low temperatures

Collision-broadened half-widths of several lines in the nu4 fundamental band of (C-12)H4 have been measured at low temperatures between 130 and 295 K using a tunable diode laser and the sweep integration technique. The broadening gases are H2, N2, He, and Ar. The temperature dependence of the measured line widths is described in terms of an exponent n, which is shown not only to be different for each broadening gas but also to depend upon the tetrahedral symmetry identification of the lines of CH4.

Varanasi, P.↗
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 NTRS1988

Quantification of several atmospheric gases from high resolution infrared solar spectra obtained at the South Pole in 1980 and 1986

High-resolution solar absorption spectra recorded at the Amundsen-Scott South Pole Station were analyzed to obtain total column amounts of O3, N2O, HNO3, CO2, CH4, and CF2Cl2, and to investigate the differences in the values obtained in December 1980 with those obtained in December 1986. In addition, vertical column amounts for HCl, NO, NO2, and C2H6 were derived for December 1986. One interesting feature of these results is that the total column amounts of HCl measured for several days at the South Pole (/6.4 + or - 0.8/ x 10 to the 15th molecules/sq cm) were high compared with the HCl column amounts reported for lower latitudes.

Goldman, Aaron↗
NASA NTRS1989

Vertical aerosol structure of Neptune - Constraints from center-to-limb profiles

New center-to-limb (CTL) equatorial region profiles of Neptune have been extracted from spatially well-resolved images. The 8900-A CTL profile entails the presence of material above the 5-mbar level whose optical depth is less than 0.5. CH4-band data admit of thin scattering hazes in the 0.4-1.5 bar pressure level, although optical depths must be lower than 0.05; so thin a haze falls short of the reflected flux at 6340 A, thereby implying the presence of another scattering layer deeper than 1.5 bars. A good fit to the observed reflectivity is obtained by a bright cloud layer with an optical depth of 3.0.

Hammel, H. B.↗
NASA NTRS1989

Pluto's atmosphere - Models based on refraction, inversion, and vapor-pressure equilibrium

Viking spacecraft radio-occultation measurements indicate that, irrespective of substantial differences, the polar ice cap regions on Mars have inversions similar to those of Pluto, and may also share vapor pressure equilibrium characteristics at the surface. This temperature-inversion phenomenon occurs in a near-surface boundary layer; surface pressure-temperature may correspond to the vapor-pressure equilibrium with CH4 ice, or the temperature may be slightly higher to match the value derived from IRAS data.

Eshleman, Von R.↗
NASA NTRS1989

Amazon capims (floating grassmats) - A source of C-13 enriched methane to the troposphere

The C-13 isotopic composition of methane emitted to the troposphere from Amazon capims (floating grassmats) ranged from -36.9 to -48.0, per mil averaging -44.4 + or - 4.2 per mil. All pools of methane associated with the grassmats were enriched; methane withdrawn from plant stems ranged from -39 to -49 per mil while bubbles stirred from the root mat averaged -41.4 per mil. As the CH4 flux from these habitats makes up some 40 percent of the total flux from the Amazon floodplain, methane emissions from the region as a whole must be enriched in.

Chanton, Jeffrey↗
NASA NTRS1989

Triton - Scattering models and surface/atmosphere constraints

Modeling of Triton's spectrum indicates a bright scattering layer of optical depth tau about 3 overlying an optically deep layer of CH4 with high absorption and little scattering. UV absorption in the spectrum indicates tau about 0.3 of red-yellow haze, although some color may also arise from complex organics partially visible on the surface. An analysis of this and other (spectro)photometric evidence indicates that Triton most likely has a bright surface, which was partially visible in 1977-1980. Geometric albedo p = 0.62 + 0.18 or - 0.12 radius r = 1480 + or - 180 km, and temperature T = 48 + or - 6 K. With scattering optical depths of 0.3-3 and about 1-10 mb of N2, a Mars-like atmospheric density and surface visibility pertain.

Thompson, W. Reid↗
NASA NTRS1989

Intensity and line width measurements in the nu(u) fundamental band of (C-13)H4

Intensities and collision-broadened line widths have been measured in the nu(u) fundamental band of (C-13)H4 at 295 K, employing the Doppler-limited spectral resolution of a tunable diode laser spectrometer and a (C-13)-enriched sample of CH4, H2, He, Ar, N2, O2, and air were chosen as the broadening gases in order to provide the data needed in atamospheric and planetary atamospheric applications.

Varanasi, Prasad↗
NASA NTRS1989

Trace gases in the Antarctic Atmosphere

Whole-air samples collected aboard the NASA ER-2 and DC-8 aircraft as part of the Airborne Antarctic Ozone Experiment were analyzed in a field laboratory set up at Punta Arenas, Chile. Mixing ratios obtained from gas chromatographic analyses of these samples are presented for CH4, CO, N2O, CFCl3, CF2Cl2, C2F3Cl3, CH3CCl3, and CCl4. A comparison of CFCl3/N2O mixing ratios from the flights of September 16-29, 1987 provides evidence of sustained subsidence.

Heidt, L. E.↗
NASA NTRS1989

Hydrogen-silicon carbide interactions

A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamic maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of Region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicon carbide is the single stable solid phase in Region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4, and SiH. Analysis of the kinetics of reaction for Region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to Regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

Eckel, Andrew J.↗
NASA NTRS1988

Ion formation by electron impact

Dissociative attachment and polar dissociation cross sections were measured for the following molecules: HC1, NO, N2O, C6H6, SiH4, Si2H6, and LiH. Direct ionization and dissociative ionization cross sections were determined for the following molecules: H2, D2, N2, O2, He, Ne, Ar, Kr, Xe, H2O, Co, CO2, CH4, SiH4, Sih4, Si2H6, N2*, and NH3. An experimental apparatus for a pulsed extraction technique was fabricated and successfully tested.

Srivastava, Santosh K.↗
NASA NTRS1989

Experimental studies of gas trapping in amorphous ice and thermal modelling of comets: Implications for Rosetta

The trapping of mixtures of CO, CH4, N2 and Ar in amorphous water ice was studied experimentally. It is shown that the ice particles could not have been formed at a higher temperature and, subsequently, cool down. Experiments where ice was deposited at elevated temperatures, then cooled down and gas was flowed into the ice, showed that the amount of trapped gas depends only on the highest temperature at which the ice was formed, or resided, prior to cooling and gas flow into it. Consequently, the cometary ice had to be formed at approx. 48 K and the ice is therefore amorphous. The thermal profile of a comet in Halley's orbit was calculated, including the build-up of an insulating dust layer. It was found that an insulating dust layer a few cm thick is enough to choke most of the water emission from the surface. A similar thermal model was calculated for comet P/Temple-1, a candidate for both CRAF and Rosetta (CNSR) missions. The temperature at a depth of 10 m is approx. 160 K for all models considered and, hence, the ice at this depth is crystalline. A crystalline ice layer 40 to 240 m thick was found to overly the gas-laden amorphous ice. Consequently, it should be difficult for the probes of the two comet missions to sample pristine amorphous ice, unless they are aimed at the bottom of an active crater.

Bar-Nun, Akiva↗