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At least 649 records · Page 36

Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

Tolbert, Margaret A.↗

Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3

Ammonium cyanate is identified as the major product of the photolysis of gaseous NH3-CO mixtures at 206.2 or 184.9 nm. Lesser amounts of urea, biurea, biuret semicarbazide, formamide and cyanide are observed. A series of 18 reactions underlying the formation of photolysis products is presented and discussed. Photocatalytic syntheses of C-14-urea, -formamide, and -formaldehyde are carried out through irradiation of (C-14)O and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. The possible contributions of the relevant reactions to the abiotic synthesis of organic nitrogen compounds on Mars, the primitive earth, and in interstellar space are examined.

Hubbard, J. S.↗

Improved Fluidized-Bed Gas Injector

Gas-injection cone in fluidized-bed reactor for coating particles with silicon or carbon cooled and protected from abrasion by stream of gas flowing over surface of cone. Hot particles entering reaction zone are coated with silicon or carbon supplied by thermal decomposition of suitable gas injected into reaction zone.

Hogle, R. A.↗

Conversion of para and ortho hydrogen in the Jovian planets

A mechanism is proposed which partially equilibrates the para and ortho rotational levels of molecular hydrogen in the atmospheres of Jupiter, Saturn, and Uranus. Catalytic reactions between the free-radical surface sites of aerosol particles and hydrogen modecules yield significant equilibration near 1 bar pressure, if the efficiency of conversion per collision is between 10 to the -8th and 10 to the -10th and the effective eddy mixing coefficient is 10,000 sq cm/sec. At lower pressures the ortho-para ratio retains the value at the top of the cloud layer, except for a very small effect from conversion in the thermosphere. The influence of conversion on the specific heat and adiabatic lapse rate is also investigated. The effect is found to be generally small, though is can rise to 10% inside the aerosol layer.

Massie, S. T.↗

Improving Hydrocarbon Separation In Gas Chromatography

Modified solica spheres enhance chromatographic separation. Commercially available silica spheres are modified by reacting them with molecules containing isocyante and isothiocyanate groups. Applications of surface derivatized spheres that result from reaction include analysis of samples prouced by atmospheric or soil probes.

Pollock, G. E.↗

Sulfur trioxide in the lower atmosphere of Venus

Inconsistencies and ambiguities are noted by the present consideration of Pioneer Venus and Venera atmospheric composition measurement of Venus in the context of lower atmosphere thermodynamic equilibrium. Among the scenarios projected on the basis of assumed correctness for selected data subsets, the O2 and SO2 concentrations reported by the Pioneer Venus chromatograph and the H2O concentrations reported by Venera 11 suggest that large concentrations of SO3 are present in the lower atmosphere of Venus. Such SO3 concentrations lead, however, to difficulties in explaining the atmosphere at and above the cloud tops, and in addition require specific assumptions concerning chemical reaction rates at and near the surface.

Craig, R. A.↗

LEO atomic oxygen effects on spacecraft materials: STS-5 results

Effects of low Earth orbit (LEO) atomic oxygen were measured on a variety of spacecraft materials which obtained exposure on STS-5. Material degradation dependency on temperature was found in one material. Of the five paints flown, only S13GLO was unaffected. Generally, the glossy paints became Lambertian and the diffuse coatings improved. Scanning electron microscope examinations indicated removal of urethane and epoxy paint binder materials. Reaction products were evident on the surfaces of Z302 paint and Mylar. Thin films showed thickness losses ranging from negligible loss in Teflon to considerable loss in Mylar and Kapton. Glossy films such as black Kapton and white Tedlar became diffused. Kevlar 29 rope lost tensile strength and silver solar cell interconnect material oxidized. Oxidation on the backside of an elevated specimen indicated that reflections of oxygen atoms were occurring and that reflecting surfaces, probably Kapton, were not fully accommodating the incident atoms.

Whitaker, A. F.↗

Ozone precursors and ozone photochemistry over eastern North Pacific during the spring of 1984 based on the NASA GTE/CITE 1 airborne observations

Simultaneous high-resolution measurements of O3, NO, CO, dew point temperature, and UV flux obtained during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation (GTE/CITE 1) spring 1984 airborne field exercise over the eastern North Pacific Ocean are analyzed. Mid-tropospheric CO, O3, and NO mixing ratios averaged about 120 parts per billion by volume (ppbv), 50 ppbv, and 10 parts per trillion by volume (pptv), respectively. Statistical analysis of the high-resolution data indicates the existence of two ozone sources, one related to the downward transport of ozone-rich air from the upper troposphere and stratosphere, and the other to the transport of ozone-rich air from the continents. Modeling calculations based on these average levels imply that, from the surface to about 8 km, photochemical reactions probably supplied a net sink of ozone to the region overlying the eastern North Pacific Ocean during the sampling period. However, because the NO levels measured during the flights were frequently at or near the detection limit of the instruments and because the results are very sensitive to the absolute NO levels and their temporal variability, the conclusion must be considered provisional.

Chameides, W. L.↗

Characterization of the surfaces of platinum/tin oxide based catalysts by Fourier Transform Infrared Spectroscopy (FTIR)

A Pt/SnO2 catalyst has been developed at NASA Langley that is effective for the oxidation of CO at room temperature (1). A mechanism has been proposed to explain the effectiveness of this catalyst (2), but most of the species involved in this mechanism have not been observed under actual catalytic conditions. A number of these species are potentially detectable by Fourier Transform Infrared Spectroscopy (FTIR), e.g., HOSnO sub x, HO sub y PtO sub z, Pt-CO, and SnHCO3. Therefore a preliminary investigation was conducted to determine what might be learned about this particular catalyst by transmission FTIR. The main advantage of FTIR for this work is that the catalyst can be examined under conditions similar to the actual catalytic conditions. This can be of critical importance since some surface species may exist only when the reaction gases are present. Another advantage of the infrared approach is that since vibrations are probed, subtle chemical details may be obtained. The main disadvantage of this approach is that FTIR is not nearly as sensitive as the Ultra High Vacuum (UHV) surface analytical techniques such as Auger, Electron Spectroscopy for Chemical Analysis (ESCA), Electron Energy Loss Spectroscopy (EELS), etc. Another problem is that the assignment of the observed infrared bands may be difficult.

Keiser, Joseph T.↗

Additives to reduce susceptibility of thermosets and thermoplastics to erosion from atomic oxygen

Polymeric materials have many attractive features such as light weight, high strength, and broad applicability in the form of films, fibers, and molded objects. In low earth orbit (LEO), these materials, when exposed on the exterior of the spacecraft, have the serious disadvantage of being susceptible to erosion by atomic oxygen (AO). AO is the most common chemical species at LEO altitudes. AO can be an extremely efficient oxidizing agent as was apparent from the extensive erosion of organic films exposed in STS missions. The mechanism for erosion involves the reaction of oxygen atoms at the surface of the substrate to form small molecular species. The susceptibility of polymeric materials varies with their chemical composition. Films with silicon atoms incorporated in the molecular structures have large coefficients of thermal expansion. This limits their utility. In an alternative approach additives were sought that mix physically and form a protective oxide layer when the film is exposed to AO. A large number of organic compounds containing silicon, germanium, or tin atoms were screened. Most were found to have very limited solubility in the polyetherimide (Ultem) films that were being protected from AO. However, one, bis(triphenyl tin) oxide, (BTO), is miscible in Ultem up to about 25 percent. Films of Ultem polyimide containing up to 25 wt percent BTO were prepared by evaporation of solvent from a solution of Ultem and BTO. The effects of AO on these films were simulated in the oxygen atmosphere of a radio frequency glow-discharge chamber. In the second part of this study, atoms were incorporated in epoxy resins. Experiments are in progress to measure the resistance of films of the cured epoxy to AO in the discharge chamber.

Orwoll, Robert A.↗

Structure of confined laminar spray diffusion flames: Numerical investigation

The structure of confined laminar spray diffusion flames is investigated numerically by solving the gas-phase conservation equations for mass species, continuity, momentum, and energy and the liquid-phase equations for droplet position, velocity, size, and temperature. A one-step global reaction scheme along with six equilibrium reactions are employed to model the flame chemistry. Monodisperse as well as polydisperse sprays are considered. The numerical results demonstrate that liquid spray flames substantially differ from gaseous flames in their structure, i.e., temperature, concentration, and velocity fields, shape, and dimensions under the same conditions. Spray flames are predicted to be taller and narrower than their counterpart gaseous ones and their shapes are almost cylindrical. This is in agreement with experimental observations. The numerical computations also show that the use of the equilibrium reactions with the one-step reaction scheme decreases the flame temperature compared to the one-step reaction scheme without the equilibrium reactions and more importantly increases the surface area of the flame zone due to a phenomenon termed 'equilibrium broadening.' The spray flames also possess a finite thickness with minimal overlap of the fuel and oxygen species. A case for which a fuel-mixture consisting of 20 to 80 percent gas-liquid by mass is introduced into the combustor is also investigated and compared with predictions using only gaseous or liquid fuel.

Mawid, M. A.↗

Workshop on chemical weathering on Mars, part 2

The third Mars Surface and Atmosphere Through Time (MSATT) Workshop, which was held 10-12 Sep. 1992, at Cocoa Beach/Cape Kennedy, focused on chemical weathering of the surface of Mars. The 30 papers presented at the workshop described studies of Martian weathering processes based on results from the Viking mission experiments, remote sensing spectroscopic measurements, studies of the shergottite, nakhlite, and chassignite (SNC) meteorites, laboratory measurements of surface analog materials, and modeling of reaction pathways. A summary of the technical sessions is presented and a list of workshop participants is included.

Burns, Roger↗

Reactions of atomic oxygen /O(3P)/ with polymer films

The reactions of polymer films with oxygen atoms are reviewed focusing on laboratory tests on polybutadienes with different amount of 1,4 or 1,2 double bonds and their polyalkenamer homologues, polyimide (Kapton), and a series of polyolefines with increasing fluorine content. It is found that etch rates increase with decrease in -CH=CH- unsaturation, starting with 1,4 -polybutadiene and reaching the maximum rate with polyethylene or ethylene-propylene rubber. IN polybutadienes with both 1,4 and 1,2 double bonds, the rate of O(3P)-induced etching is lower the higher the 1,2 content. The reactions are confined to the polymer surface.

Golub, Morton A.↗

The future of manned spaceflight

This paper examines the future of manned spaceflight in context of past accomplishments and possible future benefits of space exploration. Three technological advances mentioned are a device called the rotating wall vessel, also known as the 'bioreactor,' which allows the study of the growth of cells in three dimensions; the use of microgravity to produce high-quality electronic, magnetic, and superconducting thin films; and mining of helium-3 from the lunar surface for use in future fusion reactions with deuterium. The author then makes recommendations on how NASA should meet the challenges of manned spaceflight.

Cohen, Aaron↗

A LiF silicon sandwich counter to measure water content of planetary surfaces

The neutron counter proposed here has a long history and was commercially available in a somewhat different form. This counter would be suitable for a rover or lander since it requires a rather long measuring time for each placement. It consists of two silicon wafer charged-particle counters with a layer of Li-6F deposited on the inner surface of one. The neutron detecting reaction is Li-6(n,H-3)He-4 in which the alpha particle and the triton are emitted from the Li-6 deposit back to back. If one of the detectors sees the alpha particle, the other will see the triton. This allows one to use a coincidence technique that virtually eliminates all background. The signals from each detector can be added together so that the total energy of the reaction, Q=4.6 MeV and the kinetic energy of the neutron, can be recorded.

Drake, D. M.↗

Aerosols and Particulates Workshop Sampling Procedures and Venues Working Group Summary

The Sampling Procedures and Venues Workgroup discussed the potential venues available and issues associated with obtaining measurements. Some of the issues included Incoming Air Quality, Sampling Locations, Probes and Sample Systems. The following is a summary of the discussion of the issues and venues. The influence of inlet air to the measurement of exhaust species, especially trace chemical species, must be considered. Analysis procedures for current engine exhaust emissions regulatory measurements require adjustments for air inlet humidity. As a matter of course in scientific investigations, it is recommended that "background" measurements for any species, particulate or chemical, be performed during inlet air flow before initiation of combustion, if possible, and during the engine test period as feasible and practical. For current regulatory measurements, this would be equivalent to setting the "zero" level for conventional gas analyzers. As a minimum, it is recommended that measurements of the humidity and particulates in the incoming air be taken at the start and end of each test run. Additional measurement points taken during the run are desirable if they can be practically obtained. It was felt that the presence of trace gases in the incoming air is not a significant problem. However, investigators should consider the ambient levels and influences of local air pollution for species of interest. Desired measurement locations depend upon the investigation requirements. A complete investigation of phenomenology of particulate formation and growth requires measurements at a number of locations both within the engine and in the exhaust field downstream of the nozzle exit plane. Desirable locations for both extractive and in situ measurements include: (1) Combustion Zone (Multiple axial locations); (2) Combustor Exit (Multiple radial locations for annular combustors); (3) Turbine Stage (Inlet and exit of the stage); (4) Exit Nozzle (Multiple axial locations downstream of the nozzle). Actual locations with potential for extractive or non-intrusive measurements depend upon the test article and test configuration. Committee members expressed the importance of making investigators aware of various ports that could allow access to various stages of the existing engines. Port locations are engine si)ecific and might allow extractive sampling or innovative hybrid optical-probe access. The turbine stage region was one the most desirable locations for obtaining samples and might be accessed through boroscope ports available in some engine designs. Discussions of probes and sampling systems quickly identified issues dependent on particular measurement quantities. With general consensus, the group recommends SAE procedures for measurements and data analyses of currently regulated exhaust species (CO2, CO, THC, NO(x),) using conventional gas sampling techniques. Special procedures following sound scientific practices must be developed as required for species and/or measurement conditions not covered by SAE standards. Several issues arose concerning short lived radicals and highly reactive species. For conventional sampling, there are concerns of perturbing the sample during extraction, line losses, line-wall reactions, and chemical reactions during the sample transport to the analyzers. Sample lines coated with quartz.or other materials should be investigated for minimization of such effects. The group advocates the development of innovative probe techniques and non-intrusive optical techniques for measurement of short lived radicals and highly reactive species that cannot be sampled accurately otherwise. Two innovative probe concepts were discussed. One concept uses specially designed probes to transfer optical beams to and from a region of flow inaccessible by traditional ports or windows. The probe can perturb the flow field but must have a negligible impact on the region to be optically sampled. Such probes are referred to as hybrid probes and are under development at AEDC for measurement in the high pressure, high temperature of a combustor under development for power generation. The other concept consists of coupling an instrument directly to the probe. The probe would isolate a representative sample stream, freeze chemical reactions and direct the sample into the analyzer portion of the probe. Thus, the measurement would be performed in situ without sample line losses due either to reactions or binding at the wall surfaces. This concept was used to develop a fast, in situ, time-of-flight mass spectrometer measurement system for temporal quantification of NO in the IMPULSE facility at AEDC. Additional work is required in this area to determine the best probe and sampling technique for each species measurement requirement identified by the Trace Chemistry Working Group. A partial list of Venues was used as a baseline for discussion. Additional venues were added to the list and the list was broken out into the following categories: (1)Engines (a) Sea Level Test Stands (b) Altitude Chambers; (2) Annular Combustor Test Stands, (3) Sector Flametube Test Stands, (4) Fundamentals Rigs/Experiments.

Pachlhofer, Peter↗