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At least 181 records · Page 10

Crossed beam studies of ion-molecule reactions in methane and ammonia

A crossed-beam apparatus is used to measure the product ion velocity and angular distributions for the following ion-molecule reactions in the relative energy range from 2 to 9 eV: CH4(+) + NH3 yields NH4(+) + CH3; CH4(+) + NH3 yields CNH5(+) + H2; NH2(+) + CH4 yields CNH4(+) + H2 (or 2H); and CH3(+) + NH3 yields CNH4(+) + H2 (or 2H). These reactions are also studied by means of deuterium labeling as a further probe of the detailed reaction dynamics. Probability contour plots for the four reactions are constructed in Cartesian velocity space, and product peaks in the plots are discussed. Relative cross sections and Q values are computed for two of the reactions as well as for the corresponding deuterium-labelled reactions. The results show that the present ion-neutral condensation reactions are highly exothermic with a deep well for the internal complex, that little hydrogen scrambling occurs, and that the energy of the reactions is released mainly as internal energy, even to the extent of producing two hydrogen atoms in some cases rather than one hydrogen atom or molecule.

Smith, G. P. K.↗

Evolution of a nitrogen atmosphere on Titan

Photochemical calculations indicate that if NH3 outgassed from Titan it should have been converted to a dense N2 atmosphere during the lifetime of the satellite. A crucial step in the process involves a gas phase reaction of N2H4 with H. The most favorable conditions for this step would be the intermediate production of a CH4-H2 greenhouse capable of raising the gas temperature to 150 K. Subsequently about 20 bars of N2 could have evolved. The pressure-induced opacity of 20 bars of N2 should suffice to explain the recently measured 200 K surface temperature. Unlike the situation on Jupiter, NH3 is not recycled on Titan by reactions involving N2 or N2H4. This may explain the failure of recent attempts to detect NH3 in the upper atmosphere of Titan.

Atreya, S. K.↗

Organic chemistry on Titan

Observations of nonequilibrium phenomena on the Saturn satellite Titan indicate the occurrence of organic chemical evolution. Greenhouse and thermal inversion models of Titan's atmosphere provide environmental constraints within which various pathways for organic chemical synthesis are assessed. Experimental results and theoretical modeling studies suggest that the organic chemistry of the satellite may be dominated by two atmospheric processes: energetic-particle bombardment and photochemistry. Reactions initiated in various levels of the atmosphere by cosmic ray, Saturn wind, and solar wind particle bombardment of a CH4 - N2 atmospheric mixture can account for the C2-hydrocarbons, the UV-visible-absorbing stratospheric haze, and the reddish color of the satellite. Photochemical reactions of CH4 can also account for the presence of C2-hydrocarbons. In the lower Titan atmosphere, photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. Hot H-atom reactions initiated by photo-dissociation of NH3 can couple the chemical reactions of NH3 and CH4 and produce organic matter.

Chang, S.↗

Jupiter's atmospheric composition and cloud structure deduced from absorption bands in reflected sunlight

The spectrum of sunlight reflected by Jupiter is analyzed by comparing observations of Woodman (1979) with multiple-scattering computations. The analysis yields information on the vertical cloud structure at several latitudes and on the abundance of CH4 and NH3 in the atmosphere of Jupiter. The abundances of CH4 and NH3 suggest that all ices and rocks are overabundant on Jupiter by a factor of 2 or more, providing an important constraint on models for the formation of Jupiter from the primitive solar nebula. The pressure level of the clouds, the gaseous NH3 abundance, the mean temperature profile, and the Clausius-Clapeyron relation suggest that these clouds are predominantly ammonia crystals with the cloud bottom at 600-700 mb. A diffuse distribution of aerosols exists between 150 and 500 mb, and the spectral variation of albedo reflects a changing bulk absorption coefficient of the material composing the aerosols and is diagnostic of the aerosol composition.

Sato, M.↗

Atmospheric cycles of nitrogen oxides and ammonia

The atmospheric cycles of nitrogenous trace compounds for the Northern and Southern Hemispheres are discussed. Source strengths and destruction rates for the nitrogen oxides: NO, NO2 and HNO3 -(NOX) and ammonia (NH3) are given as a function of latitude over continents and oceans. The global amounts of NOX-N and NH3-N produced annually in the period 1950 to 1975 (34 + 5 x one trillion g NOx-N/yr and 29 + or - 6 x one trillion g NH3-N/yr) are much less than previously assumed. Globally, natural and anthropogenic emissions are of similar magnitude. The NOx emission from anthropogenic sources is 1.5 times that from natural processes in the Northern Hemisphere, whereas in the Southern Hemisphere, it is a factor of 3 or 4 less. More than 80% of atmospheric ammonia seems to be derived from excrements of domestic animals, mostly by bulk deposition: 24 + or - 9 x one trillion g NO3 -N/yr and 21 + or - 9 x one trillion g NH4+-N/yr. Another fraction may be removed by absorption on vegetation and soils.

Bottger, A.↗

Nitrogen supply system based on hydrazine dissociation

Future long-duration manned space missions will require a method of generating N2 for cabin leakage makeup and repressurization. Life Systems, working with NASA, is developing a Nitrogen Supply Subsystem (NSS) based on the dissociation of N2H4 into a mixture of H2 and N2. The latter is separated to provide the makeup N2. Recent advances in specific hardware developments have resulted in the design and fabrication of a nominal 3.6 kg/day N2 generation module. The design integrates a N2H4 catalytic dissociator, three ammonia (NH3) dissociation stages and four H2 separation stages into a 33 kg, 14 cu dm module. A technique has been devised to alternate the NH3 dissociation and H2 separation stages to give high N2 purity in the product stream. Tests have shown the product stream to contain less than 0.5 percent H2 and 20 ppm NH3. This paper discusses the development and test activities of the NSS program. It reviews the design, configuration, operation and projected performance characteristics of a 4.4 kg/day NSS suitable for NASA's planned Space Operations Center.

Heppner, D. B.↗

Kinetic inhibition of CO and N2 reduction in circumplanetary nebulae - Implications for satellite composition

In contrast to the solar nebula, the conversion of CO to CH4 and of N2 to NH3 in the circumplanetary nebulae of the Jovian planets is fast enough relative to radial mixing and nebula cooling rates that CO and N2 are minor constituents in the circumplanetary nebulae. Thus, although the Jovian planets may have accreted carbon and nitrogen from the solar nebula mainly in the form of CO and N2, these species were then reprocessed within the circumplanetary nebulae to form mainly CH4 and NH3. Satellites of the Jovian planets which accreted in sufficiently cool parts of their circumplanetary nebula are therefore predicted to retain large amounts of NH3 and CH4 in the form of clathrate hydrates and also very small but chemically important amounts of HCN.

Prinn, R. G.↗

Detection of interstellar NH sub 3 in the far-warm and dense gas in Orion-KL

The detection of the (J,K) = a(4,3) yields s(3,3) rotation inversion transition of ammonia at 124.6 microns toward the center of the Orion-KL region is reported. The line is in emission and has a FWHM or = to 30 km s 0.15. The far IR ammonia line emission probably comes mainly from the 'hot core', a compact region of warm, very dense gas previously identified by the radio inversion lines of NH3. The a(4,3) yields s(3,3) line is very optically thick, and since it is seen in emission, radiative excitation of the (4,3) NH3 level by far IR emission from dust within the source can be ruled out. Radiative excitation via the 10 microns of vibrational transitions of NH3 also seems unlikely. Hence, the (4,3) level is probably collisionally excited and the gas in the hot core region is warmer than the dust. Since the far IR line emission is highly trapped, densities of approximately 10 to the 7th power cu cm are high enough to explain the observations. Shock heating by the mass outflow from IRc2 may account for the high gas temperatures in the hot core region.

Townes, C. H.↗

Lower atmospheric composition of Jupiter from Voyager infrared measurements

The observed spectrum of Jovian atmosphere exhibits spectral features of H2, CH4, C2H6, NH3, H2O, GeH4 and CH3D. Analytical programs were developed for radiative transfer calculations and for retrieval of lower atmospheric composition of Jupiter from the observed infrared spectrum. The program models developed are based line by line transmittance calculations with appropriate convolution of the instrument function. The constituent inversion programs were evaluated for accuracy by analyzing synthetic data for retrievals of NH3 profiles. The inversion programs were employed for retrieval of NH3 profiles from the Voyager infared data with results generally in agreement with the accepted values.

Abbas, M. M.↗

The photochemistry of biogenic gases in the early and present atmosphere

The distribution of gases in the prebiologial paleoatmosphere is investigated using photochemical models. A chart of the photochemical and chemical reactions and reaction rates for CH4, NH3, H2S, N2O, and CO atmospheric gases is given. Mixing ratios and surface mixing ratios for CH4, NH3, CO, and N2O are obtained using thermodynamic equilibrium calculations; an increase in CH4 and N2O is observed. The reactions, which explain the photochemistry of the gases studied, are presented. The sources of these gases and their concentration with regards to altitude are examined. Graphs of the vertical distribution of CH4, NH3, H2S, CO, O2, and N2O in prebiological paleoatmosphere are provided. The data reveals the presence of only N2, CO2, and N2O in the early atmosphere; with the evolution of life, sources of atmospheric gases increased and their influence on the photochemistry of the troposphere and stratosphere increased.

Levine, J. S.↗

The catalysis of hydrazines

Hydrazine sulfate in a hot aqueous solution can be catalyzed in the direction of 3 N2H4 = 4 NH3 + N2. Free hydrazine in a hot aqueous solution dissociates in the presence of platinum in the following direction: 2 N2H4 = 2 NH3 + N2 + H2. In the presence of sodium hydroxide, the catalytic dissociation of hydrazine takes a third direction: 3 N2H4 = 2 NH3 + 2 N3 + 3 H2.

Tanatar, S.↗

Compatability of dispersion-strengthened platinum with resistojet propellants

Resistojets for the Space Station require long life and multipropellant capability. The choice of available materials to meet these requirements is limited. Dispersion-strengthened platinum was selected. Past results indicated that it should be suffieiently inert in candidate propellant environments and should be capable of operating at moderate temperatures for extended periods. A series of propellant compatibility tests was done with platinum strengthened with either yttria or zirconia. Data presented included the results of 1000-hr tests in CO2, H2, ammonia (NH3), N2, steam, hydrazine (N2H4), and methane (CH4); and 2000-hr tests in H2 and NH3. The platinum samples were tested at 1400 C in CO2, H2, NH3, N2, steam, and N2H4; at 500 C in CH4; and at 800 C in N2H4. The mass-loss results indicated material life, exptrapolated from experimental mass-loss data, in excess of 100 000 hr in all environments except steam and N2H4, where it was greater than or =45000 hr. Generally, on the basis of mass loss, there were no compatibility concerns in any of the environments considered. Optical and scanning electron microscopy were used to determine the effect of propellants on the material surface and to evaluate material stability.

Whalen, Margaret V.↗

Evidence for methane and ammonia in the coma of comet P/Halley

Methane and ammonia abundances in the coma of Halley are derived from Giotto ion mass spectrometer data using an Eulerian model of chemical and physical processes inside the contact surface to simulate Giotto high-intensity spectrometer ion mass spectral data for mass-to-charge ratios (m/q) from 15 to 19. The ratio m/q = 19/18 as a function of distance from the nucleus is not reproduced by a model for a pure water coma. It is necessary to include the presence of NH3, and uniquely NH3, in coma gases in order to explain the data. A ratio of production rates Q(NH3)/Q(H2O) = 0.01 = 0.02 results in model values approximating the Giotto data. Methane is identified as the most probable source of the distinct peak at m/q = 15. The observations are fit best with Q(CH4)/Q(Q2O) = 0.02. The chemical composition of the comet nucleus implied by these production rate ratios is unlike that of the outer planets. On the other hand, there are also significant differences from observations of gas phase interstellar material.

Allen, M.↗

H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.

Tsang, T.↗

High-temperature shock formation of N2 and organics on primordial Titan

Theoretical models suggest that the initial form of nitrogen in Titan's atmosphere may have been NH3. The possible importance of strong shocks produced during high-velocity impacts accompanying the late stages of accretion are investigated as a method for converting NH3 to N2, of which Titan's atmosphere is now primarily composed. The focused beam of a high-power laser is used to simulate the effects of an impact in Titan's atmosphere. For mixtures of 10, 50, and 90 percent NH3, yields of 0.25, 1, and 6 x 20 to the 17th molecules of N2 per joule, respectively, were obtained. It is also found that the yield of HCN is comparable to that for N2. Several other hydrocarbons are produced, many with yields in excess of theoretical high-temperature-equilibrium models. The above yields, when combined with models of the satellite's accretion, result in a total N2 production comparable to that present in TItan's atmosphere and putative ocean.

Mckay, Christopher P.↗

On the ammonia abundance in the coma of Halley's Comet

Consideration is given to recent work by Allen et al. (1987) which suggests that the value of the ratio of the abundance of the atomic masses 19 to 18 observed in situ in the inner coma of Comet Halley is incompatible with a pure H2O nucleus and requires an NH3 abundance of 1-2 percent. The present authors discuss possible ways of explaining the radial profile of r = 19/18, which deemphasizes the presence of NH3. It is shown that the observed value of the 19/18 mass ratio in the inner coma does not necessarily imply the existence of a significant abundance of NH3. An elevated UV flux, for which there is circumstantial evidence, could produce the same effect.

Marconi, M. L.↗

The nitrogen cycle on Mars

Nirtogen is an essential element for the evolution of life, because it is found in a variety of biologically important molecules. Therefore, N is an important element to study from a exobiological perspective. In particular, fixed nitrogen is the biologically useful form of nitrogen. Fixed nitrogen is generally defines as NH3, NH4(+), NO(x), or N that is chemically bound to either inorganic or organic molecules, and releasable by hydrolysis to NH3 or NH4(+). On Earth, the vast majority of nitrogen exists as N2 in the atmosphere, and not in the fixes form. On early Mars the same situations probably existed. The partial pressure of N2 on early Mars was thought to be 18 mb, significantly less than that of Earth. Dinitrogen can be fixed abiotically by several mechanisms. These mechanisms include thernal shock from meteoritic infall and lightning, as well as the interaction of light and sand containing TiO2 which produces NH3 that would be rapidly destroyed by photolysis and reaction with OH radicals. These mechanisms could have been operative on primitive Mars.The chemical processes effecting these compounds and possible ways of fixing or burying N in the Martian environment are described. Data gathered in this laboratory suggest that the low abundance of nitrogen along (compared to primitive Earth) may not significantly deter the origin and early evolution of a nitrogen utilizing organisms. However, the conditions on current Mars with respect to nitrogen are quite different, and organisms may not be able to utilize all of the available nitrogen.

Mancinelli, Rocco L.↗