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At least 469 records · Page 26

Chemical evolution. XL - Clay-mediated oxidation of diaminomaleonitrile

The inhibition of the oligomerization of HCN by montmorillonite clays is shown to be caused by oxidation of diaminomaleonitrile (DAMN) by ferric ion in the clay lattice, with ferrous ion and oxalic acid the reaction products. It is demonstrated that diiminosuccinonitrile is the initial reaction product and is rapidly hydrolized to oxalic acid and HCN. The same oxidative transformations are effected by ferric ion bound to Dowex 50, ferric ion in solution, and Ni(NH3)6(2+). The rate of reaction of DAMN indicates no catalytic role for the clay in the oxidation of DAMN, and little reaction of the latter was observed with montmorillonite in which the bulk of the iron was in the divalent state. The possible significance of these redox reactions to chemical evolution is discussed.

Ferris, J. P.↗

Chemistry and evolution of Titan's atmosphere

The chemistry and evolution of Titan's atmosphere are reviewed, in light of the scientific findings from the Voyager mission. It is argued that the present N2 atmosphere may be Titan's initial atmosphere, rather than one photochemically derived from an original NH3 atmosphere. The escape rate of hydrogen from Titan is controlled by photochemical production from hydrocarbons. CH4 is irreversibly converted to less hydrogen-rich hydrocarbons, which over geologic time accumulate on the surface to a layer thickness of about 0.5 km. Magnetospheric electrons interacting with Titan's exosphere may dissociate enough N2 into hot, escaping N atoms to remove about 0.2 of Titan's present atmosphere over geologic time. The energy dissipation of magnetospheric electrons exceeds solar EUV energy deposition in Titan's atmosphere by an order of magnitude, and is the principal driver of nitrogen photochemistry. The environmental conditions in Titan's upper atmosphere are favorable to building up complex molecules, particularly in the north polar cap region.

Strobel, D. F.↗

Spatially resolved methane band photometry of Saturn. I - Absolute reflectivity and center-to-limb variations in the 6190-, 7250-, and 8900-A bands

Spatially resolved measurements of Saturn's absolute reflectivity in methane bands at 6190, 7250, and 8900 A and in nearby continuum regions are presented. Images were obtained through narrow-band interference filters with a 500 x 500-pixel charge-coupled device. Band/continuum ratios were measured to high accuracy by referencing to the ring brightness in each image. Several data processing techniques enhanced the quality of the observations. These are the use of the ring symmetry to find center position and orientation, accurate subtraction of ring light, and constrained image deconvolution. Uncertainty in the continuum absolute reflectivity is within 10%. Uncertainties in band/continuum ratios are from one to several percent. The Equatorial Zone was much brighter than any other latitude in the strong 8900 band image. Northern midlatitudes were brighter than southern midlatitudes. The latter observation indicates fewer high-altitude aerosols in the south, a possible result of atmospheric dynamics or seasonal sublimation of NH3 crystals. The data are tabulated and presented in a form suitable for quantitative scattering model analyses.

West, R. A.↗

Preliminary submillimeter spectroscopic measurements using a submillimeter heterodyne radiometer

A submillimeter heterodyne radiometer uses a submillimeter laser, pumped by a CO2 laser, as a local oscillator and a room temperature Schottky barrier diode as the first IF mixer. The radiometer can resolve spectral lines in the submillimeter region of the spectrum (arising from pure rotational molecular transitions) to within 0.3 MHz, using acousto-optic spectrum analyzer which measures the power spectrum by simultaneously sampling 0.3 MHz wide channels over a 100 MHz bandwidth spanning the line. Preliminary observations of eight spectral lines of H2O2, CO, NH3 and H2O, all lying in the 434-524 micrometer wavelength range are described. All eight lines were observed using two local oscillator frequencies obtained by operating the submillimeter laser with either methyl fluoride (CH3F) or formic acid (HCOOH) as the lasing gas. Sample calculations of line parameters from the observed data show good agreement with established values. One development goal is the size and weight reduction of the package to make it suitable for balloon or shuttle experiments to detect trace gases in the upper atmosphere.

Safren, H. G.↗

Theoretical studies of photodissociation of small molecules of astrophysical importance

The radicals and ions observed in comets result from photodissociation and photoionization of molecules. According to current models, a comet is composed chiefly of a large, solid nucelus of frozen gases (parent molecules) such as H2O, HCN, and NH3. It is believed comets were formed at the same time and in the same region of space as the major planets and that their chemical composition is the same as that of the early solar system. As the comet nears the Sun, the surface heats up, liberating the frozen gases as well as dust particles. Solar radiation photodissociates the parent molecules into fragments that are observed by resonance fluorescence. Both polyatomic molecules, present in the interstellar medium, and cometary radicals were observed. Using laboratory photo-dissociation data and computer models, astronomers are attempting to identify the parent molecules that account for all observed radicals and ions.

Saxon, R. P.↗

The infrared spectral properties of frozen volatiles

Since Whipple's dirty snowball model of comet nuclei, it has been generally accepted that volatile ices help to explain cometary phenomena. The infrared spectral properties of many substances that are potential candidates for frozen volatiles in the solar system are being pursued; indeed some of these frozen materials have been found in the solar system: H2O, CO2, and SO2. A review of laboratory spectra in the range 1 to 20 microns of H2O, CO2, SO2, CH4, NH3, H2S, CO, NH4HS and NH3.H2O is presented. Both reflection spectra of thick frosts and transmission spectra of thin films are shown, and their main characteristics are described. Hydrates, clathrates, and composite spectra are discussed. When it is possible to observe the nuclei of comets at close range, it may be possible to identify frozen volatiles by their infrared spectra.

Fink, U.↗

Model calculations of the molecular composition of interstellar grain mantles

A chemical reaction scheme comprising gas phase as well as grain surface reactions is used for the numerical calculation of the chemical composition of mantles accreting on interstellar grains. The composition of the growing grain mantle is determined on the basis of the relative accretion rates of the gas phase molecules and diffusion-controlled surface reactions. Results show that grain mantles generally consist of the molecules H2O, H2CO, N2, O2, CO, CO2, H2O2, and NH3. A detailed examination of the formation of H2 on grain surfaces leads to the conclusion that it proceeds through hydrogen abstraction from such molecules as H2CO, H2S, N2H2, and N2H4. The IR characteristics of the calculated grain mantles are discussed with emphasis on the observed ice band at the 3250/cm wavelength.

Tielens, A. G. G. M.↗

The atmospheres of Io and other satellites

Voyager measurements of gaseous SO2 in a hot spot region and of ions of sulfur, oxygen, and SO2(+) in the plasma torus, combined with the groundbased measurements of SO2 frost on the surface, indicate that SO2 is perhaps the dominant constituent of Io's atmosphere. Indeed the ionosphere of Io can be sustained by a pure SO2 atmosphere in thermal equilibrium with the surface. Upper limits on common volatiles H2O, CO2, NH3, and CH4 and exceedingly small, although S2 and Ar may still be present. Photochemistry of SO2 could lead to O2 as the major gas on the night side. Reasonable processes for loss to the torus include thermal escape, sputtering, and sweep-up of ions. The symmetry of the sodium cloud between eastern and western elongation is difficult to reconcile with any substantial, diurnally varying atmosphere. Europa, Ganymede, and Callisto may have oxygen atmospheres resulting from photolysis of water vapor. A pressure of approximately 10 to the -6th microbar is predicted, consistent with the Voyager upper limit for Ganymede. A much higher pressure might be present if the water vapor pressure is increased by a low albedo (Callisto) or sputtering (Europa).

Kumar, S.↗

Thermodynamics of silicon nitridation - Effect of hydrogen

Equilibrium compositions for the nitridization of Si were calculated to detect the effectiveness of H2 in removal of the oxide film and in increasing the concentration of SiO and reducing the proportions of O2. Gibbs free energy for the formation of SiN2O was computed above 1685 K, and at lower temperatures. The thermodynamic properties of SiN2O2 were then considered from 1000-3000 K, taking into account the known thermodynamic data for 39 molecular combinations of the Si, Ni, and O. The gases formed were assumed ideal mixtures with pure phase condensed species. The mole fractions were obtained for a system of SiO2 with each Si particle covered with a thin layer of SiO2 before nitridation, and a system in which the nitriding atmosphere had access to the Si. The presence of H2 was determined to enhance the removal of NiO2 in the first system, decrease the partial pressure of O2, increase the partial pressures of SiO, Si, H2O, NH3, and SiH4, while its effects were negligible in the Si system.

Shaw, N. J.↗

Visual and infrared observations of the distant Comets P/Stephan-Oterma /1980g/, Panther /1980u/, and Bowell /1980b/

The paper reports combined visual imagery and spectroscopy, near-infrared spectroscopy, and broadband infrared photometry of comets P/Stephan-Oterma (1980g), Bowell (1980b), and Panther (1980u) at intermediate heliocentric distances. The visual data indicate the existence of solid grains in extended halos around the nuclei of the three comets. Broadband near-infrared and thermal infrared measurements of Comet Panther suggest the presence of 2-4-micron-radius particles in the coma which most likely contain molecules incorporating the N-H bond, but which are more complex and less volatile than NH3. Such molecules can be produced in the grains by cosmic-ray reprocessing. Near infrared spectral features identical to those seen in comet Panther similary suggest the presence of a molecule incorporating the N-H bond in comet Bowell.

Jewitt, D. C.↗

An analysis of the reflection spectrum of Jupiter from 1500 A to 1740 A

The Jovian reflection spectrum was modeled to determine the mixing ratios of C2H2, the upper limits to mixing ratios of C2H4, C4H2, and NH3, to detect the amount of dust in the stratosphere, and to measure the intensity of the H2 Lyman band dayglow emission. Data were gathered by the IUE spacecraft in the wavelength regions 1500 A to 1740 A, concentrating in the 10 mbar pressure region. Detailed Jupiter model parameters are provided. The mixing ratios of C2H2, C2H6, and C4H2 were found to be near 10 to the -7th, 6.6 x 10 to the -6th, and 2.9 x 10 to the -10th, respectively. Comparisons made with the Voyager 1 and 2 data indicated that the scale height of C2H2 in the 150-10 mbar region is double that of the bulk atmosphere. The data are significant for photochemical modeling of the upper Jovian atmosphere.

Gladstone, G. R.↗

Laboratory simulation of tunable diode laser remote measurement of atmospheric gases using topographic targets

In order to test the possibility that tunable diode laser (TDL) systems using topographic targets can be applied to the measurement of a variety of gases at concentrations and distances characteristic of industrial gas leaks, a single-ended TDL system was assembled for use with selected topographic targets to detect NO2 at atmospheric pressure and NO2 and NH3 at low pressures. In both cases, the intensity distribution of radiation backscattered from selected targets was found to be heavily weighted to a specular rather than a Lambertian distribution. A sensitivity of 5 ppm-m has been demonstrated for the case of NO2.

Webster, C. R.↗

New far infrared observations of the central 30 arcmin of the Galaxy

Observations of the 55 micron and 125 micron emissions of the central 30 arcmin of the Galaxy were performed with 1 arcmin resolution with instrumentation on-board the Kuiper flying observatory. The flux distributions detected showed both wavelengths with peaks near the galactic center, some extension along the galactic plane, and the 125 micron feature located 30 arcsec south. An asymmetry was found around Sgr A, and the variation in dust temperature across the region was calculated from the ratio of the two wavelengths. The temperature peak was around Sgr A, with subsidiary peaks associated with the 55 micron emission. A common heating source was indicated by correlations between cm wavelength sources and the temperature maps. Additionally, the distributions of NH3 and formaldehyde were also correlated with the dust distribution at the center.

Dent, W. A.↗

CO2 DIAL sensitivity studies for measurements of atmospheric trace gases

An analysis is presented of the accuracy of infrared differential absorption lidar (DIAL) measurements of trace constituents in the atmosphere. Expressions are derived for the signal-to-noise ratios applicable in the detection of a signal from a scattering cell for the cases of single-detection heterodyne detection and direct detection. Results of computer simulations of the expectation value of the measured return for various measurement conditions are presented which illustrate the sensitivities of plume measurements for horizontal range-resolved and vertical content measurements of NH3 in heterodyne and direct detection. Advantages for long-range measurements of the use of rare isotope laser frequencies, tuning by collision broadening, and closely spaced on and off frequencies are pointed out.

Brockman, P.↗

High pressure cosmochemistry applied to major planetary interiors: Experimental studies

Progress is reported in the development of the P-T-X diagram for 0 less than or = X less than or = 0.50 and in the development of techniques for measuring adiabats of phases of NH3-H2O. The partial phase diagram is presented, investigations of the compositions of ammonia ices are described, and methods for obtaining the infrared spectra of ices are discussed.

Nicol, M. F.↗

Extensions of suspension systems to measure effects of hypokinesia/hypodynamia and antiorthostasis in rats

Suspension systems are used to simulate hypokinetic/hypodynamic (H/H) and anitorthostatic (AO) responses seen under conditions of weightlessness. Growing rats in H/H suspension with unloaded hindlimbs for one and two weeks respond with muscle atrophy and increased excretion of nitrogenous end products such as urea, NH3 and 3 methyl histidine. Since muscle is in a dynamic state of synthesis and breakdown of protein, relationships between protein, RNA and DNA contents in the four muscles which reflect weight bearing and non-weight bearing functions were assessed. Protein and RNA progressively decreased over a one and two week period of H/H suspension: soleus gastrocnemius=plantaris EDL. Concommitant analysis of DNA contents showed there were no changes. The interpretation was that protein synthesis was slowed during H/H. As with muscle mass, protein and RNA levels recovered rapidly after removal from H/H. The AO rats (which are also H/H) respond with diuresis, natriuresis and kaliuresis in a manner comparable to responses seen when thoracic blood vessels are volume loaded.

Musacchia, X. J.↗

Radical and ion molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in RF plasmas at low pressures ( 1.0 torr)

The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.

Avni, R.↗

The composition of interstellar grain mantles

The molecular composition of interstellar grain mantles employing gas phase as well as grain surface reactions is studied. The calculated mixtures consist mainly of the molecules H2O, H2CO, N2, CO, O2, CO2, H2O2, NH3, and their deuterated counterparts in varying ratios. The exact compositions depend strongly on the physical conditions in the gas phase. The calculated mixtures are compared to the observations by using laboratory spectra of grain mantle analogs. The two are in reasonable agreement except for the strength of the 6.8-micrometers band. A possible solution for this discrepancy is discussed. Finally, future observations are suggested which may shed further light on the composition of interstellar grain mantles.

Tielens, Alexander G. G. M.↗