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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 271 records · Page 15
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NASA NTRS1986

Application of an atmospheric pressure sampling mass spectrometer to chlorination reactions

An atmospheric pressure mass spectrometric sampling system, based on a free jet expansion was used to study certain M-Cl-O reactions at high temperatures. The apparatus enables the volatile species from a 1-atm chemical process to be directly identified with a mass spectrometer which operates at approx. 10 to the minus 8th power torr. Studies for both pure metals and alloys are discussed. It is shown that this mass spectrometer system aids in identifying the volatile species, and provides fundamental information on the reaction mechanism.

Jacobson, N. S.↗
NASA NTRS1986

Infrared line intensities of chlorine monoxide

Absolute infrared line intensities of several ClO lines in the rotational-vibrational (1-0) band were measured using infrared heterodyne spectroscopy near 12 microns. A measurement technique using combined ultraviolet absorption and infrared line measurements near 9.5 microns and 12 microns permitted an accurate determination of the column densities of O3 and ClO in the absorption cell and thus improved ClO line intensities. Results indicate ClO line and band intensities approximately 2.4 times lower than previous experimental results. Effects of possible failure of local thermodynamic equilibrium conditions in the absorption cell and the implication of the results for stratospheric ClO measurements in the infrared are discussed.

Kostiuk, T.↗
NASA NTRS1986

Reductions of Antarctic ozone due to synergistic interactions of chlorine and bromine

The vertical column density of ozone observed in October over Antarctica has fallen precipitously over the past 10 yr. The concentration at Halley Bay (76 deg S, 27 deg W), expressed conventionally in Dobson units (DU), has dropped from about 300 DU in 1975 to less than 200 DU in 1984. Values in 1985 were even lower, comparable with the lowest values recorded anywhere on earth. It is suggested here that the loss of O3 in Antarctica may be attributed to catalysis of O3 recombination by a scheme in which the rate-limiting step is defined by the reaction of ClO + BrO - Cl + Br + O2. Concentrations of NO2 must be low and heterogeneous reactions involving particles in the polar stratospheric clouds must be an important element of the relevant chemistry. Industrial sources make important contributions to the contemporary budgets of both BrO and ClO and are likely to grow significantly in the future.

Mcelroy, M. B.↗
NASA NTRS1986

The Antarctic ozone minimum - Relationship to odd nitrogen, odd chlorine, the final warming, and the 11-year solar cycle

Photochemical calculations along 'diabatic trajectories' in the meridional phase are used to search for the cause of the dramatic springtime minimum in Antarctic column ozone. The results indicate that the minimum is principally due to catalytic destruction of ozone by high levels of total odd nitrogen. Calculations suggest that these levels of odd nitrogen are transported within the polar vortex and during the polar night from the middle to upper stratosphere and lower mesosphere to the lower stratosphere. The possibility that these levels are related to the 11-year solar cycle and are increased by enhanced formation in the thermosphere and mesosphere during solar maximum conditions is discussed.

Callis, L. B.↗
NASA NTRS1986

The formation of volatile corrosion products during the mixed oxidation-chlorination of cobalt at 650 C

The reaction of cobalt with 1 pct Cl2 in 1, 10, and 50 pct O2/Ar atmospheres has been studied at 650 C with thermogravimetry and mass spectrometry. The principal vapor species appear to be CoCl2 and CoCl3. In all cases, CoCl2(s) forms at the oxide/metal interface and equilibration of the volatile chlorides with Co3O4 does not occur in the early stages of the reaction. In the 1 pct Cl2 1 pct O2-Ar case, continuous volatilization occurs. In the 1 pct Cl2-10 pct O2-Ar and 1 pct CL2-50 pct O2-Ar cases, volatilization occurs only in the first few minutes of reaction. Afterwards, the reaction is predominantly oxidation.

Jacobson, N. S.↗
NASA NTRS1988

Antarctic chlorine chemistry - Possible global implications

Occurrence of heterogeneous reactions on the surface of polar stratospheric clouds (PSC) is a necessary component of the Cl-related chemical mechanisms proposed to explain the recently observed decrease of O3 during Antarctic spring. A one-dimensional model is used to assess the impact of these heterogeneous reactions on future global O3 trends if they were to occur on the global aerosol layer. The impact of these reactions on the concentration of Cl species in the present-day atmosphere is also calculated. The reaction (ClNO3 + HCl) could have a large impact on stratospheric O3. A fast rate for this reaction would greatly enhance the present concentration of ClO and reduce the abundance of HCl in the lower stratosphere. Because of the large differences between the Antarctic and global environments, the calculated global O3 trends are smaller than those calculated for Antarctica.

Rodriguez, Jose M.↗
NASA NTRS1988

In situ observations of ClO in the Antarctic: Evidence for chlorine catalyzed destruction of ozone

Results from a series of 12 ER-2 aircraft flights into the Antarctic polar vortex are summarized. These in situ data define the spatial and temporal distribution of ClO as the aircraft flew at an altitude of approx. 18 km from Punta Arenas (54 deg S latitude) to the base of the Palmer Peninsula (72 deg S latitude), executed a rapid descent to approx. 13 km, turned north and climbed bach to approximately 18 km, returning to Punta Arenas. A general pattern in the ClO distribution is reported: mixing ratios of approximately 10 ppt are found at altitude in the vicinity of 55 deg S increasing to 50 ppt at 60 degrees S. In the vicinity of 65 deg S latitude a steep gradient in the ClO mixing ratio is observed. At a fixed potential temperature, the ClO mixing ratio through this sharp transition increases by an order of magnitude within a very few degrees of latitude, thus defining the edge of the chemical containment vessel. From the edge of that containment vessel to the southern extension of the flights, 72 deg S, a dome of slowly increasing ClO best describes the distribution. Conclusion are drawn from the data.

Anderson, J. G.↗
NASA NTRS1989

Chemistry and transport in a three-dimensional stratospheric model - Chlorine species during a simulated stratospheric warming

The distributions in the stratosphere of a variety of chemical species were calculated for a 6-day period during the February 1979 stratospheric major warming, using winds derived from a spectral forecast model which included O(x), NO(x), HO(x), and ClO(x) chemistries as well as longitudinally varying reaction rate coefficients and photolysis rates for these molecules. The results obtained indicate a particular importance of chemistry and transport for the Cl-containing species ClO, ClONO2, HCl, and HOCl. Dynamical effects dominate the variability of HCl, while diurnal effects dominate that of ClONO2 and ClO. The effects of strong planetary wave activity may be seen in terms of large longitudinal variability of the total HCl and ClONO columns in the stratosphere; in the middle and high northern latitudes, it is sufficiently large to exceed the diurnal variability of the column.

Kaye, Jack A.↗
NASA NTRS1989

Ozone destruction by chlorine radicals within the Antarctic vortex - The spatial and temporal evolution of ClO-O3 anticorrelation based on in situ ER-2 data

The chemical evolution of the Antarctic vortex region was studied during August 23-September 22, 1987 on the basis of in situ O3 and ClO data collected by the ER-2 aircraft. Particular attention is given to the evolution of the ClO-O3 anticorrelation from the first flight on August 23, 1987, which penetrated well into the vortex, through the course of 10 flights culminating on September 22, 1987. It is concluded that the disappearance of ozone within the Antarctic vortex results from halogen-catalyzed recombination of O3 to molecular oxygen.

Anderson, J. G.↗
NASA NTRS1989

Mass spectrometric observations of metal oxychlorides produced by oxidation-chlorination reactions

It was recently reported that Cr2O3-forming alloys show less corrosion resistance than Al2O3-forming alloys in Cl2/O2 mixtures, which is attributed to the formation of porous Cr2O3 scales and stable CrO2Cl2 vapor species. This paper reports the results of direct mass spectrometric observations with a high-pressure sampling mass spectrometer of these metal oxychlorides forming on the surfaces of Hastelloy S and Alloy 600 superalloys. Samples were preoxidized for 2 hrs at 900 C before the exposure to a O2/Ar gas mixture containing 1 percent Cl2. Results of X-ray diffraction showed scales containing Cr2O3 and NiCr2O4 on both alloys. After exposure to Cl2, large quantities of Cr2O2Cl2 were demonstrated for both alloys, indicating that this is a route for the breakdown of Cr2O3 scales. The Mo present in the Hastelloy S leads to more rapid attack by Cl2, resulting in the formation of MoO2Cl2.

Jacobson, N. S.↗
NASA NTRS1990

Effects of atmospheric transport on column abundances of nitrogen and chlorine compounds in the arctic stratosphere

In the absence of heterogeneous processes, distributions of NO(y), HNO3, Cl(x) and HCl in the polar winter stratosphere should be determined by transport. A model simulating distributions of these species in the arctic for January and February 1989 is developed using observed fields of potential vorticity and potential temperature. Comparison of model results with column measurements from the DC-8 indicates conversion of NO(x) to HNO3, condensation of HNO3, conversion of HCl to CINO3, and conversion of HCl plus CINO3 to an unmeasured species. Heterogeneous processes strongly affect abundances of NO(y) and Cl(x) species in the winter arctic stratosphere.

Yatteau, John H.↗
NASA NTRS1990

Formation and decay of (3P(J))O atoms in the laser flash photolysis of chlorine dioxide (OClO) at 308 nm

The quantum yields of O(3P(J)) and Cl(2P(3/2)) atoms released in the laser flash photolysis of OClO at 308 and 298 K were determined and the kinetics of the subsequent oxygen atom decay was investigated using time-resolved atomic resonance fluorescence measurements. The results are consistent with the formation of sym-ClO3 having a Delta Hf(ClO3) (formed in the reaction O + OClO + Ar) of 55.6 +/-4 kcal/mol.

Colussi, A. J.↗
NASA NTRS1992

The 1985 chlorine and fluorine inventories in the stratosphere based on ATMOS observations at 30 deg North latitude

Results are presented of an investigation of the Cl and F inventories derived from the concentrations of eleven Cl- and F-bearing organic and inorganic species throughout the atmosphere, based on observations with the Atmospheric Trace Molecule Spectroscopy instrument aboard the Space Shuttle during the Spacelab 3 mission of April 29 to May 6, 1985. It was found that, in April-May 1985, near 30 deg N, the mean total stratospheric concentrations of Cl and F were 2.58 +/-0.10 ppbv and 1.15 +/-0.12 ppbv, respectively. Partitioning among the source, sink, and reservoir species was consistent with the conservation of the F and Cl budgets throughout the stratosphere. It is shown that the budgets of Cl and F above about 45 km altitude can be determined accurately by measuring only HCl, HF, and CF4 and provide a straightforward timely reference point for future inventories and trends evaluations.

Zander, R.↗
NASA NTRS1992

Search for infrared absorption lines of atmospheric chlorine monoxide (ClO)

A search for features of the ClO (1-0) vibration-rotation band has been conducted based on a 5000 signal-to-rms noise ratio IR spectrum derived by coadding 39 high-quality 0.0053/cm resolution solar spectra recorded with the McMath Fourier transform spectrometer on Kitt Peak. Evidence for absorption has been found at the locations of several of the stronger ClO P-branch lines with minimal interference. Detailed results are presented for the P(8.5) and P(7.5) 2Pi3/2-2Pi3/2 lines of Cl-35O at 833.2974 and 834.6249/cm, respectively. If ClO is present in the stratosphere at the concentrations indicated by other methods, our analysis indicates that modest improvements in signal-to-noise ratio and spectral resolution would permit a definitive detection of ClO in IR ground-based spectra.

Rinsland, Curtis P.↗
NASA NTRS1993

Chlorine catalyzed destruction of ozone - Implications for ozone variability in the upper stratosphere

The annual mean and the annual amplitude of ozone have been derived from ozone measurements from the SBUV and SBUV/2 spectrometers on board the Nimbus-7 and NOAA-11 satellites. These values differ significantly from values calculated using a two-dimensional model of stratospheric photochemistry and dynamics with standard chemistry. We have found that the differences between the calculated and data-derived values are considerably improved by changing the partitioning in the Cly family to create a larger reservoir of HCl and reducing ClO. This is accomplished by including a channel for the products HCl + O2 from the reaction ClO + OH in addition to the products Cl + HO2. This partitioning also improves the agreement between the calculated and measured values of ClO/HCl ratio.

Chandra, Sushil↗
NASA NTRS1991

Heterogeneous reactions of chlorine nitrate and hydrogen chloride on type I polar stratospheric clouds

A fast-flow reactor coupled with a quadrupole mass spectrometer was used to study the heterogeneous reactions ClONO2 + HCl yields Cl2 + HNO3 (1) and ClONO2 + H2O yields HOCl + HNO3 (2) on vapor-deposited HNO3-H2O ice substrates. It was found that the sticking coefficient of HCl on these substrates was a strong function of the substrate composition, ranging from about 2 x 10 exp -5 at nitric acid trihydrate composition to 6 x 10 exp -3 at 45 wt pct HNO3. The HNO3-H2O ice substrates were found to have large internal surface areas, and corrections for gas-phase diffusion within the porous ices were applied to observed loss rates.

Leu, Ming-Taun↗
NASA NTRS1993

Ab initio study of the chlorine nitrate protonation reaction - Implications for loss of ClONO2 in the stratosphere

Ab initio quantum mechanical methods, including coupled-cluster theory, are used to determine the equilibrium geometries, dipole moments, and harmonic vibrational frequencies of ClONO2, NO2(+), and four isomers of protonated ClONO2. It was found that, for the equilibrium structures and harmonic frequencies of ClONO2, HOCl, and NO2(+), the highest-level theoretical predictions are consistent with the available experimental information concerning the reactions of ClONO2 and HOCl with HCl on the surface of polar stratospheric clouds (PSCs). The study supports a recent hypothesis that the reaction of ClONO2 on the surface of PSCs is proton catalyzed, although the mechanism is different.

Lee, Timothy J.↗