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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

Results of a comprehensive study of the photochemistry of N2(+) in the ionosphere

The improved match that can be obtained between the Atmospheric Explorer (AE) data on the ionospheric F layer N2(+) abundance and theoretical predictions by changing the dissociative recombination rate coefficient is demonstrated. Historically, models have overestimated the N2(+) concentration. It is shown that the calculated enhancement is due to charge exchange between 0(+)(2D) with N2. Increasing alpha by a factor of 2-3, at least in the orbits examined, can augment the destruction of vibrationally excited N2(+) ions. However, the validity of the correction is dependent on the availability of further laboratory data.

Abdou, W. A.↗
NASA NTRS1985

Martian atmospheric photochemistry and composition during periods of low obliquity

During periods of low obliquity, previous work has shown that martian CO2 partial pressures decreased to 0.1 mbar; CO2 partial pressures decreased to 0.02 mbar prior to the formation of the Tharsis bulge. The permanent polar caps act as a cold trap and projected global average water vapor abundances drop to possibly as low as 0.00001 precipitable micron. As a result, the odd hydrogen catalytic cycle would not be effective at recombining CO and O back into CO2, and as much as 0.12 mbar of CO and 0.06 mbar of O2 could exist. These increased abundances would radically affect surface oxidation, change the lower atmospheric thermal structure, and completely alter the upper atmosphere.

Lindner, B. L.↗
NASA NTRS1986

The production of trace gases by photochemistry and lightning in the early atmosphere

Recent atmospheric calculation suggest that the prebiological atmosphere was most probably composed of nitrogen, carbon dioxide, and water vapor, resulting from volatile outgassing, as opposed to the older view of a strongly reducing early atmosphere composed of methane, ammonia, and hydrogen. Photochemical calculations indicate that methane would have been readily destroyed via reaction with the hydroxyl radical produced from water vapor and that ammonia would have been readily lost via photolysis and rainout. The rapid loss of methane and ammonia, coupled with the absence of a significant source of these gases, suggest that atmospheric methane and ammonia were very short lived, if they were present at all. An early atmosphere of N2, CO2, and H2O is stable and leads to the chemical production of a number of atmospheric species of biological significance, including oxygen, ozone, carbon monoxide, formaldehyde, and hydrogen cyanide. Using a photochemical model of the early atmosphere, the chemical productionof these species over a wide range of atmospheric parameters were investigated. These calculations indicate that early atmospheric levels of O3 were significantly below the levels needed to provide UV shielding. The fate of volcanically emitted sulfur species, e.g., sulfur dioxide and hydrogen sulfide, was investigated in the early atmosphere to assess their UV shielding properties. The photochemical calculations show that these species were of insufficient levels, due in part to their short photochemical lifetimes, to provide UV shielding.

Levine, J. S.↗
NASA NTRS1985

Kinetics and photochemistry Golden, D. M.

The data for chemical kinetics rate constants and photochemical cross sections taken from a compilation prepared in early 1985, entitled Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, is presented.

Demore, W. B.↗
NASA NTRS1985

Parameterization of the photochemistry of stratospheric ozone including catalytic loss processes

A parameterization has been developed which accurately describes the photochemical response of odd oxygen to dynamically induced perturbations in odd oxygen and temperature. The temperature and odd oxygen dependencies of the loss processes for odd oxygen through catalytic cycles involving odd nitrogen, odd chlorine, and odd hydrogen have been specifically included. The assumption that a linear perturbation equation may be used to describe the response of odd oxygen to perturbations in odd oxygen and temperature has been tested and found to be acceptable for a physically reasonable range of perturbations, i.e., up to approximately 50 percent in odd oxygen mixing ratio and approximately 10 K in temperature. The scheme should prove useful for analyzing the feedback between ozone chemistry and ozone transport and also for analysis of ozone and temperature data.

Stolarski, R. S.↗
NASA NTRS1986

Stratospheric photochemical studies using Nimbus 7 data. I - Ozone photochemistry. II - Development of inferred trace specie distributions

The present investigation has the objective to make use of the limb infrared monitor of the stratosphere (LIMS) data set in conducting stratospheric photochemical studies. A description of the data is provided. The data are utilized in a zero-dimensional model incorporating the relevant chemistry. The chemical reaction scheme considered is a subset of the scheme used in the Langley one-dimensional model discussed by Callis et al. (1983). Attention is given to a comparison of model results and data, a model uncertainty analysis, model response to modifications in rate data, the ozone-temperature relationship, and the diurnal variation in the upper stratospheric ozone.

Natarajan, M.↗
NASA NTRS1986

On the atmospheric photochemistry of nitric acid

Measurements of the temporal and spatial variations in HNO3, particularly those from the Nimbus 7 limb IR monitor of the stratosphere (LIMS) satellite experiment, are compared to both a two-dimensional chemical/dynamical model and to chemistry/parcel trajectory analyses. Significant discrepancies are found between the observed and modeled variations in the winter season, especially in the polar night region. The study of the evolution of HNO3 suggests that an important source exists for this species in the high-latitude winter stratosphere that is not included in presently accepted photochemical schemes. Possible reactions to account for this discrepancy are explored.

Austin, J.↗
NASA NTRS1986

Theoretical analysis of isotope effects on ozone formation in oxygen photochemistry

In situ measurements of stratospheric ozone and laboratory studies of ozone production in electric discharge through oxygen have shown previously that ozone containing heavy isotopes of oxygen (O-17, O-18) may be formed preferentially. In order to assess the relevance of thee latter experiment to the stratospheric measurements, detailed understanding of the effect of isotopic substitution on the O3 formation reaction O + O2 + M yields O3 + M and on the O atom exchange reaction O + O2 + O yields O2 + O is necessary. In this work, an estimate of the effect of isotopic substitution on the recombination rate is made by us of approximate dynamical theories and statistical mechanics. The results indicate the possibility of isotope effects on the O + O2 recombination rate of the order of several percent at stratospheric temperatures. In general, recombination reactions involving heavy (mass 49, 50) O3 formation are found to be slower than the reaction leading to normal (mass 48) O3 formation. The calculated isotope effects are sufficiently small that the uncertainties in the model input and the approximations in the dynamical theories will probably make the quantitative nature of these results subject to considerable uncertainty. This isotope effect should not be observable in the atmosphere given the precision of the current measurements but may be crucial in the understanding of the laboratory experiments, where observed enhancements are only of the order of several percent. Possible reasons for this discrepancy between the observed enhancement and predicted depletion are presented.

Kaye, J. A.↗
NASA NTRS1986

The young sun, the early earth and the photochemistry of oxygen, ozone and formaldehyde in the early atmosphere

Recent work on the evolution of the solar nebula and the subsequent formation of planets is reviewed, and the stages of star formation thought to lead to a protosun and an accompanying solar nebula are considered. Photochemical results suggest that concentrations of O2, O3, and H2CO, and the ratio of CO/CO2 in the prebiological paleoatmosphere are very sensitive to atmospheric levels of H2O and CO2 and to the flux of incident solar ultraviolet. For enhanced levels of CO2 and solar UV, surface levels of O2 may have approached the parts per billion level in the prebiological paleoatmosphere. It is suggested that 10 percent or more of the enhanced H2CO production could have been rained out of the atmosphere into the early oceans where synthesis into more complex organic molecules could have taken place. CO/CO2 values of greater than unity could have been possible for enhanced levels of solar UV flux.

Canuto, V. M.↗
NASA NTRS1987

Model ozone photochemistry on the basis of Solar Mesosphere Explorer mesospheric observations

Morning and afternoon mesospheric ozone profiles (50-90 km) measured by the Solar Mesosphere Explorer (SME) satellite are analyzed with one-dimensional photochemical models. The observed ozone abundances are 40 percent and 100 percent greater than the model ozone abundances at 50 and 80 km, respectively. Diurnal model calculations are compared with SME observations of ozone profiles at about 0400 and 1400 LT for high northern summer latitudes. Analysis of the ratios of these early morning and midafternoon ozone profiles provides the additional constraint that larger odd-oxygen production rates are required if lower odd-hydrogen activity is invoked to increase model O3 abundances. The increase in odd-oxygen production must be solar zenith angle independent in the mesosphere, ruling out significant changes in the Schumann-Runge band O2 opacities from Allen and Frederrick (1982).

Clancy, R. T.↗
NASA NTRS1987

Photochemistry and molecular ions in carbon-rich circumstellar envelopes

An earlier theory of ionization of C-rich circumstellar envelopes based on the photochemical model is extended to include the temperature dependence of ion-molecule reactions with polar molecules, particularly HCN, and line self-shielding of CO dissociating radiation. The results are applied to the abundances of HCO(+) and HNC in C-rich circumstellar envelopes. With standard parameters for IRC + 10216, the model is found to be consistent with the new upper limit to the antenna temperature of the J = 1-0 line of HCO(+) obtained with the IRAM 30-m telescope. The photochemical model provides a natural explanation of the relatively large ratio of HCN to HNC observed for C-rich circumstellar envelopes, and good agreement is obtained for the H(C-13)N/HNC antenna temperature ratio measured for IRC + 10216.

Glassgold, A. E.↗
NASA NTRS1987

Photochemistry and molecular ions in oxygen-rich circumstellar envelopes

A theory for the ionization of the circumstellar envelopes around O-rich red giants is developed from the photochemical model. The main source of ionization is photoionization of H2O, OH, and C by the interstellar UV radiation field, supplemented by cosmic-ray ionization of hydrogen. Significant amounts of H3O(+) and HCO(+) are produced, with peak abundances of about 10 to the -7th at intermediate distances from the star. Although H3O(+) may be difficult to detect with current instrumentation, HCO(+) is probably detectable in nearby O-rich envelopes with large millimeter-wave telescopes.

Mamon, G. A.↗
NASA NTRS1987

An update of nitrile photochemistry on Titan

Comparisons are undertaken between laboratory kinetics experiments and Voyager observations in order to shed light on possible chemical reaction pathways to the generation of cyanogen and dicyanoacetylene in Titan's upper atmosphere. The predicted concentrations of the simple nitrile compounds are found to be of a magnitude realistically corresponding to the Voyager observations.

Yung, Yuk L.↗
NASA NTRS1988

Photochemistry of biogenic emissions over the Amazon forest

The boundary layer chemistry over the Amazon forest during the dry season is simulated with a photochemical model. Results are in good agreement with measurements of isoprene, NO, ozone, and organic acids. Photochemical reactions of biogenic isoprene and NOx can supply most of the ozone observed in the boundary layer. Production of ozone is very sensitive to the availability of NOx, but is insensitive to the isoprene source strength. High concentrations of total odd nitrogen (NOy) are predicted for the planetary boundary layer, about 1 ppb in the mixed layer and 0.75 ppb in the convective cloud layer. Most of the odd nitrogen is present as PAN-type species, which are removed by dry deposition to the forest. The observed daytime variations of isoprene are explained by a strong dependence of the isoprene emission flux on sun angle. Nighttime losses of isoprene exceed rates of reaction with NO3 and O3 and appear to reflect dry-deposition processes. The 24-hour averaged isoprene emission flux is calculated to be 38 mg/sq m per day. Photooxidation of isoprene could account for a large fraction of the CO enrichment observed in the boundary layer under unpolluted conditions and could constitute an important atmospheric source of formic acid, methacrylic acid, and pyruvic acid.

Jacob, Daniel J.↗
NASA NTRS1988

Stability and photochemistry of ClO dimers formed at low temperature in the gas phase

The recent observations of elevated concentrations of the ClO radical in the austral spring over Antarctica have implicated catalytic destruction by chlorine in the large depletions seen in the total ozone column. One of the chemical theories consistent with an elevated concentration of the ClO is a cycle involving the formation of the ClO dimer through the association reaction: ClO + ClO = Cl2O2 and the photolysis of the dimer to give the active Cl species necessary for O3 depletion. Here, researchers report experimental studies designed to characterize the dimer of ClO formed by the association reaction at low temperatures. ClO was produced by static photolysis of several different precursor systems: Cl sub 2 + O sub 3; Cl sub 2 O sub 2; OClO + Cl sub 2 O spectroscopy in the U.V. region, which allowed the time dependence of Cl sub 2, Cl sub 2 O, ClO, OClO, O sub 3 and other absorbing molecules to be determined.

Cox, R. A.↗
NASA NTRS1988

Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

The role of chlorine atoms in the oxidation of methane and nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere was investigated using a one-dimensional photochemical model that incorporated the chemistry of CH4, NMHCs, NO(x), O(x), and HO(x), as well as organic and inorganic halogens in the troposphere and lower stratosphere. The model predicted that chlorine atoms are present in the marine troposphere at the concentrations of about 1000/cu cm, mostly as a product of the reaction between OH and HCl released from sea spray. The results indicate that Cl atoms cause 20 to 40 percent of NMHC oxidation in the troposphere and 40 to 90 percent in the lower stratosphere. At 15 km, the NMHC-Cl reactions account for nearly 80 percent of the PAN produced. Where available, experimental data confirmed the model predictions.

Singh, H. B.↗
NASA NTRS1989

Infrared spectroscopy of astrophysical ices - New insights in the photochemistry

The photochemical effects of the interstellar radiation field on the ice mantles of molecular-cloud dust grains are investigated by means of laboratory simulations. The apparatus and analytical methods described by Hagen et al. (1979) and Hagen (1982) are employed, and the results are presented as spectra and discussed in detail. Consideration is given to the strong IR absorption bands of OCN(-) and NH4(+) which appear after photolysis and heating of H2O/NH3/CO/O2 ices, the detection of similar bands toward W33A, the critical role of NH3 in the photochemical production of ions, and the use of calculated integrated absorption-band strengths to estimate astrophysical column densities.

Grim, R. J. A.↗