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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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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1974

Spectroscopy and reactions of molecules important in chemical evolution

The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

Becker, R. S.↗
NASA NTRS1978

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.↗
NASA NTRS1971

Variable photosynthetic units, energy transfer and light-induced evolution of hydrogen in algae and bacteria.

The present state of knowledge regarding the truly photochemical reactions in photosynthesis is considered. Nine-tenths of the available knowledge is of a biochemical nature. Questions regarding the activities of the chlorophyll system are examined. The simplest photochemical response observed in living hydrogen-adapted algal cells is the release of molecular hydrogen, which continues even after all other known natural reactions have been eliminated either by heating or the action of poisons.

Gaffron, H.↗
NASA NTRS1983

Latitudinal variation of tropospheric ozone in a photochemical model

A zonally, vertically, and annually averaged numerical model of trace gases in the troposphere is used to examine the variation of ozone as a function of latitude. Processes included in the ozone budget are a source due to downward transport of ozone from the stratosphere, deposition at earth's surface, north-south diffusive transport, and photochemical reactions. Sensitivity of calculated ozone concentrations to the latitude variation and magnitude of the stratospheric source is presented. The model indicates a net photochemical source of ozone in the Northern Hemisphere and a net chemical sink in the tropical latitudes. Calculated variation of ozone concentration with latitude is in qualitative agreement with observations.

Hameed, S.↗
NASA NTRS2005

Investigation of the Reactions and Distribution of Polycyclic Aromatic Hydrocarbons and Fullerenes in Extraterrestrial Material

The work funded by this research grant includes four specific projects: (1) Mapping the spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. (2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe laser-desorption laser-ionization mass spectrometry ( pL2MS) and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. (3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. (4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames.

Zare, Richard N.↗
NASA NTRS1989

Photochemistry of the atmosphere of Uranus

A detailed one-dimensional photochemical model incorporating vertical transport by eddy and molecular diffusion is used to study the importance of chemical and physical processes that control the hydrocarbon abundances in the stratosphere of Uranus. The study includes updated photochemical reaction rates and photolysis branching ratios; explicit calculation of the condensation rate of condensing species; and appropriate boundary conditions at the tropopause. It is found that the basic photochemical process generally produces low net conversion efficiencies of methane to higher hydrocarbons. However, even with these low efficiencies, the total condensation rate, which represents the net rate of conversion of methane to hydrocarbons, is roughly 2 x 10 to the -16th g/cm sec, in agreement with the upper range of the low condensation rate for the production of the stratospheric aerosol layer as determined by Pollack et al. (1987). Furthermore, a range of vertical transport rates is required to separately match the observational constraints on hydrocarbon abundances. The solar reflection data refer to the sunlit polar region of Uranus and require an eddy diffusion coefficient of K approx. = 50 sq cm/sec for globally averaged insolation or K approx = 1500 (Nh/N) exp 1/2 for overhead sun. The Voyager 2 Utraviolet Spectrometer solar occultation data refer to the equatorial regions, thus implying a large latitudinal gradient in stratospheric hydrocarbon abundance.

Summers, Michael E.↗
NASA NTRS1989

Venus volcanism: Rate estimates from laboratory studies of sulfur gas-solid reactions

Thermochemical reactions between sulfur-bearing gases in the atmosphere of Venus and calcium-, iron-, magnesium-, and sulfur-bearing minerals on the surface of Venus are an integral part of a hypothesized cycle of thermochemical and photochemical reactions responsible for the maintenance of the global sulfuric acid cloud cover on Venus. SO2 is continually removed from the Venus atmosphere by reaction with calcium bearing minerals on the planet's surface. The rate of volcanism required to balance SO2 depletion by reactions with calcium bearing minerals on the Venus surface can therefore be deduced from a knowledge of the relevant gas-solid reaction rates combined with reasonable assumptions about the sulfur content of the erupted material (gas + magma). A laboratory program was carried out to measure the rates of reaction between SO2 and possible crustal minerals on Venus. The reaction of CaCO3(calcite) + SO2 yields CaSO4 (anhydrite) + CO was studied. Brief results are given.

Ehlers, K.↗
NASA NTRS1984

The nitrogen cycle: Atmosphere interactions

Atmospheric interactions involving the nitrogen species are varied and complex. These interactions include photochemical reactions, initiated by the absorption of solar photons and chemical kinetic reactions, which involve both homogeneous (gas-to-gas reactions) and heterogeneous (gas-to-particle) reactions. Another important atmospheric interaction is the production of nitrogen oxides by atmospheric lightning. The nitrogen cycle strongly couples the biosphere and atmosphere. Many nitrogen species are produced by biogenic processes. Once in the atmosphere nitrogen oxides are photochemically and chemically transformed to nitrates, which are returned to the biosphere via precipitation, dry deposition and aerosols to close the biosphere-atmosphere nitrogen cycle. The sources, sinks and photochemistry/chemistry of the nitrogen species; atmospheric nitrogen species; souces and sinks of nitrous oxide; sources; sinks and photochemistry/chemistry of ammonia; seasonal variation of the vertical distribution of ammonia in the troposphere; surface and atmospheric sources of the nitrogen species, and seasonal variation of ground level ammonia are summarized.

Levine, J. S.↗
NASA NTRS1993

Multiple steady states in atmospheric chemistry

The equations describing the distributions and concentrations of trace species are nonlinear and may thus possess more than one solution. This paper develops methods for searching for multiple physical solutions to chemical continuity equations and applies these to subsets of equations describing tropospheric chemistry. The calculations are carried out with a box model and use two basic strategies. The first strategy is a 'search' method. This involves fixing model parameters at specified values, choosing a wide range of initial guesses at a solution, and using a Newton-Raphson technique to determine if different initial points converge to different solutions. The second strategy involves a set of techniques known as homotopy methods. These do not require an initial guess, are globally convergent, and are guaranteed, in principle, to find all solutions of the continuity equations. The first method is efficient but essentially 'hit or miss' in the sense that it cannot guarantee that all solutions which may exist will be found. The second method is computationally burdensome but can, in principle, determine all the solutions of a photochemical system. Multiple solutions have been found for models that contain a basic complement of photochemical reactions involving O(x), HO(x), NO(x), and CH4. In the present calculations, transitions occur between stable branches of a multiple solution set as a control parameter is varied. These transitions are manifestations of hysteresis phenomena in the photochemical system and may be triggered by increasing the NO flux or decreasing the CH4 flux from current mean tropospheric levels.

Stewart, Richard W.↗
NASA NTRS1979

Organic chemistry on Titan

Features taken from various models of Titan's atmosphere are combined in a working composite model that provides environmental constraints within which different pathways for organic chemical synthesis are determined. Experimental results and theoretical modeling suggest that the organic chemistry of the satellite is dominated by two processes: photochemistry and energetic particle bombardment. Photochemical reactions of CH4 in the upper atmosphere can account for the presence of C2 hydrocarbons. Reactions initiated at various levels of the atmosphere by cosmic rays, Saturn 'wind', and solar wind particle bombardment of a CH4-N2 atmospheric mixture can account for the UV-visible absorbing stratospheric haze, the reddish appearance of the satellite, and some of the C2 hydrocarbons. In the lower atmosphere photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. It is concluded that the surface of Titan may contain ancient or recent organic matter (or both) produced in the atmosphere.

Chang, S.↗
NASA NTRS1993

Eddy mixing coefficient upper limit derived from the photochemical balance of O2

This work is based on the study of the photochemical balance of molecular oxygen in the martian atmosphere by using a one-dimensional model of photochemical reactions involving species derived from CO2 and H2O. The model is basically similar to one used previously for the study of the regulation of CO on a global scale, but the chemical rates are taken from another source. In the present scheme, the regulation of molecular oxygen is studied over timescales of the order of its photochemical lifetime (approximately equals 30 yr), which is much shorter than typical escape timescales. Thus, the escape fluxes are fixed to the values given by 3 and 4. We examine the calculated equilibrium abundances of O2 for given thermal, eddy diffusion coefficients and H2O profiles. The thermal profile is taken from in the lower atmosphere. At higher levels, in order to include the diurnal and seasonal thermal profile variability, we have also used the IRTM data. In order to study the influence of both temperature and pressure profiles on the O2 mixing ratio, we have made several tests corresponding to different martian seasons. The results show that the influence of pressure and temperature is quantitatively weak compared to the one of K and of the water vapor density (H2O). Thus, in the following we have fixed the pressure at the surface to a value of 7 mbar and we have used unique standard thermal profile corresponding to a profile roughly averaged over the year, the season, and the day: T equal 205 K at 0 km altitude, 175 K at 25 km, and 145 K at 50 km.

Rosenqvist, J.↗
NASA NTRS1989

Photochemistry of CO and H2O - Analysis of laboratory experiments and applications to the prebiotic earth's atmosphere

The role photochemical reactions in the early earth's atmosphere played in the prebiotic synthesis of simple organic molecules was examined, extending an earlier calculation of formaldehyde production rates to more reduced carbon species, such as methanol, methane, and acetaldehyde. The experimental results of Bar-Nun and Chang (1983) are simulated as an aid in the construction of the photochemical scheme and as a way of validating the model. The results indicate that some fraction of CO2 and H2 present in the primitive atmosphere could have been converted to simple organic molecules. The exact amount is dependent on the partial pressure of CO2 and H2 in the atmosphere and on what assumptions are made concerning the shape of the absorption spectra of CO2 and H2O.

Wen, Jun-Shan↗
NASA NTRS1980

The chemistry and transport of methane and carbon monoxide in the troposphere

The present understanding of the physical and chemical behavior of methane, carbon monoxide and the chemical species involved in the conversion of CH4 to CO in the troposphere is reviewed. Following a brief summary of CO and CH4 emission and reactions in urban areas, attention is given to measurements of the spatial and temporal distributions of CO and CH4 in the rural atmosphere, the contribution of the oceans to atmospheric CO and CH4 concentrations, and interactions of CH4 and CO with soils and vegetation. Estimates of the transport of CH4 and CO from the troposphere to the stratosphere are discussed, and photochemical reactions of the constituents are examined. Two- and three-dimensional models for CH4 and CO transport are presented, and possible future variations in atmospheric abundances of the molecules are considered. Finally, present estimates of the global methane and carbon dioxide budgets are summarized, and it is pointed out that, despite the large contribution of anthropogenic sources, the budgets appear to be in balance.

Peters, L. K.↗
NASA NTRS1980

Stratospheric ozone decrease due to chlorofluoromethane photolysis - Predictions of latitude dependence

A two-dimensional model is used to predict the 1990 reduction in ozone due to the chlorine compounds formed by chlorofluoromethane (CFM) photolysis when the CFM release rate is held constant at the 1975 value. The predicted globally averaged ozone reduction of 3.5% is similar to that predicted by one-dimensional models that did not include chlorine nitrate chemistry, and used lower values for the reactions rates of NO + HO2 yielding NO2 + OH and O3 + HO2 yielding OH + 2O2. When the 5.7 ppbv increase in chlorine compounds predicted by one-dimensional models to occur under steady-state conditions is simulated by the two-dimensional model, a 26% decrease in atmospheric ozone is predicted. The latitude dependence of the ozone reduction is discussed in terms of the relevant photochemical reaction and transport. The chemical reactions that most strongly influence the meridional dependence of the ozone depletion are identified as those associated with the reactions of chlorine monoxide and atomic oxygen, the recombination of ozone and atomic oxygen, and the photodissociation of molecular oxygen.

Borucki, W. J.↗
NASA NTRS1983

Photochemistry of methane in the earth's early atmosphere

The photochemical behavior of methane in the early terrestrial atmosphere is investigated with a detailed model in order to determine how much CH4 might have been present and what types of higher hydroocarbons could have been formed. It is found that any primordial methane accumulated during the course of earth accretion would have been dissipated by photochemical reactions in the atmosphere in a geologically short period of time after the segregation of the core. Abiotic sources of methane are not likely to have been large enough to sustain CH4 mixing ratios as high as 10 to the -6th, the threshold for a possible methane greenhouse, with a CO-rich atmosphere being a possible exception. After the origin of life an increasing biogenic source of methane may have driven CH4 mixing ratios well above 10 to the 6th. The rise of atmospheric oxygen in the early Proterozoic may have led to a more rapid photochemical destruction of methane, lowering the mixing ratio to its present value.

Kasting, J. F.↗
NASA NTRS1991

Detection of solid methanol toward W33A

A recently detected absorption feature at 3.53 microns in the spectrum of W33A has been assigned to methanol (CH3OH). Its optical depth implies that methanol is the second most abundant molecule (7 percent relative to H2O) in the grain mantles in the line of sight toward W33A observed to date. Laboratory experiments have shown that the implied abundance is difficult to explain by UV irradiation of the dust grains alone. Grain surface reactions or condensation directly out of the gas phase must also play roles, but the relative contributions of the various processes are difficult to estimate. The optical depth of the 3.53-micron feature constrains the contribution of methanol to the 6.8-micron feature in W33A to be 10 percent or less, requiring the contribution of at least one other compound to this feature, while the estimated contribution to the 4.9-micron absorption band is even smaller. Only a small contribution of formaldehyde (H2CO) is consistent with the observed 3.53-micron band profile. In contrast to methanol, formaldehyde can be produced readily by photochemical reactions within the ice mantle.

Grim, R. J. A.↗
NASA NTRS1998

Contrast Between 1992 and 1997 High Latitude Spring Haloe Observations of Lower Stratospheric HCl

HCl measurements from HALOE in the northern hemisphere during mid-May 1997 revealed vortex fragments in which the chlorine reservoir partitioning was strongly pushed toward HCl (approx. 90% HCl, approx. 10% ClONO2), similar to partitioning previously observed in the Antarctic vortex region. In contrast, observations of ClONO2 and HCl in the northern polar spring, 1992, and in other years, show these species established the balance typical for gas phase photochemical reactions in this region (approx. 60% HCl, approx. 40% ClONO2). Annually, chlorine reservoirs in the winter lower stratosphere polar vortex are converted to chlorine radicals via heterogeneous reactions on particle surfaces at very cold temperatures (less than about 200 K). As temperatures warm in spring, the heterogeneous processes become insignificant compared with gas phase reactions, and the chlorine reservoirs are reformed. Measurements through the northern winter/spring in 1992 show rapid formation of ClONO2, followed by steady loss of ClONO2 and increasing HCl. Although ClONO2 measurements are not available for 1997, the HCl increase in 1997 is observed to be much more rapid and the eventual HCl mixing ratio is about 50% greater than that of 1992. The observations are examined through comparison with the Goddard three-dimensional chemistry and transport model. This model utilizes winds and temperatures from the Goddard Earth Observing System Data Assimilation System and a complete integration scheme for stratospheric photochemistry. Analysis of the evolution of HCl and ClONO2 shows that the observed difference in the overall rate of HCl formation is explained by the sensitivity of the gas-phase chemistry to the ozone mixing ratio and the temperature. The results show that the model accurately simulates HCl and ClONO2 evolution during these two winters. Model validity is further supported by comparisons with O3 and reactive nitrogen species NO and NO2. This analysis provides a sensitive test of the lower stratospheric chlorine photochemistry, particularly because the analysis considers constituent evolution at a time when the HCl and ClONO2 are far from a photochemical stationary state.

Douglass, A. R.↗