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At least 145 records · Page 8

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.↗

Quantification of Changes in Thermospheric O/N2 from Observations of UV Airglow and Aurora

The primary goal of the proposed research was to use images from the Ultraviolet Imager (UVI) as remote monitors of changes in the ratio of thermospheric O to N2 at high latitudes in response to geomagnetic disturbances. The principal project tasks were to select UVI image data, develop and extend modeling/analysis tools, and, finally, correlate observed changes with geomagnetic activity. In particular, it was necessary to model the average expected dayglow surface to isolate changes from storms. Note that this research differs significantly from previous efforts in that the 'quiet-time' dayglow surface is modeled from first principles rather than being developed empirically from observations. This technique should thus be more generally applicable to observations from other missions.

Germany, G. A.↗

Biomolecular Effects of Cold Plasma Exposure

The effects of cold plasma exposure on Deinococcus radiodurans, plasmid DNA and model proteins were assessed using microbiological, spectrometric and biochemical techniques. Exposure of D. radiodurans, an extremely radiation resistant microbe, to O2 plasma (less than or equal to 25 W, approx. 45 mTorr, 90 min) yielded a approx. 99.999 % sterilization and the sterilization rate was increased approx. 10-fold at 100 W and 500 mTorr. AFM images shows that the exposed cells are significantly deformed and possess 50-70 nm concavities. IR analysis indicates the chemical degradation of lipids, proteins and carotenoids of the cell wall and membrane. Intracellular damage was indicated by major absorbance loss at 1245, 1651 and 1538/cm corresponding to degradation of DNA and proteins, respectively. Biochemical experiments demonstrate that plasmas induce strand scissions and crosslinking of plasmid DNA, and reduction of enzyme activity; the degradation is power dependent with total sample loss occurring in 60 s at 200 W and 500 mTorr. Emission spectroscopy shows that D. radiodurans is volatilized into CO2, CO, N2 and H2O confirming the removal of biological matter from contaminated surfaces. The O2 plasma impacts several cellular components predominantly through chemical degradation by atomic oxygen. A CO2, plasma, however, was not effective at degrading D. radiodurans, revealing the importance of plasma composition, which has implications for planetary protection and the contamination of Mars.

Mogul, Rakesh↗

Interpretation of Dynamics Explorer far UV images of the quiet time thermosphere

A selected set of far ultra violet images of Earth have been analyzed quanitatively to establish their validity for studying thermospheric weather. The set of images chosen for the study was restricted to mostly geomagnetically quiet conditions in order to obtain a baseline understanding of the relationship between the observations and thermospheric phenomenology. The images included low to modrerate solar activity levels. A new model was developed to generate global dayglow images using first principles methods. The mass Spectrometer/incoherent scatter (MSIS-86) model was used to predict the thermospheric concentrations. The analyses of thermospheric images observed in the 123 to 160-nm nominal passband show that the spectral composition for observations on the projected earth disk is dominated by O I 130.4-nm radiation (85-90%), with concentrations from O I 135.6-nm and N2 Lyman-Birge-Hopefield (LBH) bands of about 5-8% each. The synthetic images reproduce the global features of the observed images rather well. Differences between the model and the data are attributed to real atmospheric effects, such as atomic oxygen depletions which are not well reproduced by the MSIS model when geomagnetic activity is elevated. The absoute values recorded were 38-54% higher than predicted. We attribute this discrepancy to low values of the solar extreme ultraviolet irradiances used in the model. Images obtained in the 136 to 165-nm nominal passband are a factor of 2.7 greater than the model. The excess signal observed is most likely due to a long wavelength tail in the instrument sensitivity which allowed Rayleigh scattered sunlight between 180and 250nm to be detected. The understanding of the Dynamics Explorer (DE 1) images gained by this study provides the basis for future work on the global response of the theremosphere to geomagnetic forcing.

Meier, R. R.↗

Wavelike perturbations observed in the neutral thermosphere of Venus

Wavelike perturbations are evident in the neutral thermosphere measurements of He, N, O, N2, and CO2 by the Pioneer Venus orbiter neutral mass spectrometer. In the wavelength range from 100 to 600 km, the amplitudes of the various species are comparable in magnitude, with CO2 having the largest amplitude, and with helium out of phase with respect to the heavier species. On the dayside, the small-scale variations of CO2 and N2 increase with increasing altitude from 170 to 210 km, with CO2 having the largest slope. Simple and complex wave structures are observed, including wave trains and pulselike events. There is more activity during nighttime than during daytime, and larger values of the activity occur in the vicinity of the predawn and postdusk terminator sectors. Below 160 km, the standard deviation of the CO2 density on the nightside is 12 percent, about 3 times the daytime value. The data are consistent with the interpretation that the density perturbation are due to gravity waves propagating upward from the lower thermosphere.

Kasprzak, W. T.↗

Studies of the aurorally-induced ultraviolet emissions on the nightside of Venus

The effect of a monoenergetic flux of electrons on a model atmosphere of the nightside thermosphere of Venus was examined. The neutral model chosen is that of Hedin for high solar activity and l65 degrees solar zenith angle. The model is based on measurements made by the Pioneer Venus Orbiter Neutral Mass Spectrometer. Four species were included in the calculation: CO2, O, CO, and N2. The numerical method that was chosen for energy deposition of the primary electrons is the continuous slowing down approximation. The secondary electron distribution was computed using the empirically determined shape of the differential cross section.

Fox, J. L.↗

Determining the Overpotential of Electrochemical Fuel Synthesis Mediated by Molecular Catalysts: Recommended Practices, Standard Reduction Potentials, and Challenges

Molecular catalysts capable of performing electrochemical transformations are frequently utilized in the synthesis of fuels. A common benchmark for evaluating catalysts for electrochemical reactions is overpotential (η) and minimizing η remains an active goal in catalysis. This Review details approaches for the determination of thermodynamic potentials for common fuel-forming reactions and for the determination of electrochemical overpotential, and underscores the need to employ methods that enable meaningful comparisons between molecular catalysts. Strategies for minimizing overpotential while maintaining high activity are highlighted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Fe on Co-Based SiO2Al2O3 Mixed Support Catalyst for Fischer–Tropsch Synthesis in 3D-Printed SS Microchannel Microreactor

This research explores the effect of a composite support of SiO2 and Al2O3 with Fe and Co incorporated as catalysts for Fischer–Tropsch synthesis (FTS) using a 3D-printed stainless steel (SS) microchannel microreactor. Two mesoporous catalysts, FeCo/SiO2Al2O3 and Co/SiO2Al2O3, were synthesized via a one-pot (OP) method and extensively characterized using N2 physisorption, XRD, SEM, TEM, H2-TPR, TGA-DSC, FTIR, and XPS. H2-TPR results revealed that the synthesis method significantly affected the reducibility of metal oxides, thereby influencing the formation of active FTS sites. SEM-EDS and TEM further revealed a well-defined hexagonal matrix with a porous surface morphology and uniform metal ion distribution. FTS reactions, carried out in the 200–350 °C temperature range at 20 bar with a H2/CO molar ratio of 2:1, exhibited the highest activity for FeCo/SiO2Al2O3, with up to 80% CO conversion. Long-term stability was evaluated by monitoring the catalyst performance for 30 h on stream at 320 °C under identical reaction conditions. The catalyst was initially active for the methanation reaction for up to 15 h, after which the selectivity for CH4 declined. Correspondingly, the C4+ selectivity increased after 15 h of time-on-stream, indicating a shift in the product distribution toward longer-chain hydrocarbons. This trend suggests that the catalyst undergoes gradual activation or restructuring under reaction conditions, which enhances chain growth over time. The increase in C4+ products may be attributed to the stabilization of the active sites and suppression of methane or light hydrocarbon formation.

Biochemistry & Molecular Biology↗

Time-Dependent Structure of the Upper Atmosphere

The physical properties of the upper atmosphere are determined mainly by heat conduction, the heat sources and the barometric law. An analysis of the integro-differential equation which describes these physical processes has been carried out. It is found that heating of the thermosphere due to absorption of the solar extreme ultraviolet (EUV) radiation alone cannot explain the observed diurnal variation of density and temperature, since it would yield a maximum of these properties at about 17h local time, instead of 14h where it is observed. Secondly, if the EUV flux is adjusted to give the observed average temperature, then the diurnal variation in density would be much too large compared with the observed amplitude. Thirdly, it would require an extremely high efficiency for the conversion of EUV radiation into heat, if we compare the required flux with Hinteregger's measurements of the EUV flux. Thus, it is necessary to have another heat source in addition to the heating due to absorption of EUV radiation. If an additional beat source is used, which has a maximum at about 9h local time and a flux of 1 erg cm−1 sec−1, a time-dependent model of the upper atmosphere is obtained that is in good agreement with the observed densities. There is evidence that this additional heat source derives its energy ultimately from the solar corpuscular radiation. In this paper we present the results of calculations for a model in the equatorial and temperature zones of the earth, for those times when the average solar activity corresponds to a solar radiation flux of 200×110−22 Wm−2 (cps)−1 at 10.7-cm wavelength. The physical properties (temperature, density, pressure, scale height, mean molecular weight and the number densities of N2, O2, O, He and H) are given as a function of local time and for the altitudes between 120 km and 2050 km.

ATMOSPHERE↗

Application of physical adsorption thermodynamics to heterogeneous chemistry on polar stratospheric clouds

Laboratory isotherms for the binding of several nonheterogeneously active atmospheric gases and for HCl to water ice are translated into adsorptive equilibrium constants and surface enthalpies. Extrapolation to polar conditions through the Clausius Clapeyron relation yields coverage estimates below the percent level for N2, Ar, CO2, and CO, suggesting that the crystal faces of type II stratospheric cloud particles may be regarded as clean with respect to these species. For HCl, and perhaps HF and HNO3, estimates rise to several percent, and the adsorbed layer may offer acid or proton sources alternate to the bulk solid for heterogeneous reactions with stratospheric nitrates. Measurements are lacking for many key atmospheric molecules on water ice, and almost entirely for nitric acid trihydrate as substrate. Adsorptive equilibria enter into gas to particle mass flux descriptions, and the binding energy determines rates for desorption of, and encounter between, potential surface reactants.

Elliott, Scott↗

Some aspects of stratospheric chemical response to solar particle precipitations. I - Potential roles of N2/A3Sigma/ and ion-chemistry

Large amounts of long lived N2(A3Sigma) are created by the energy degradation of precipitating solar particles. Laboratory data suggest that in the stratosphere N2(A3Sigma) are efficiently converted into N2O. Through reactions with O(1D), N2O may gradually release NO and thereby influence the long term aspects of stratospheric chemical response. During the daytime, negative ions may transform an active NO(x) into an inactive HNO3. At night both negative and positive ion chemistry generate HO(x). Omission of ionic chemistry results in considerable underestimation of O3 depletion during the initial phases of solar particle events, and thereby introduces significant error in the estimation of the nature of the prompt response.

Prasad, S. S.↗

Composition, Structure and Evolution of Uranian and Neptunian Satellites

Large uncertainties in the current estimated densities of all of these satellites prevent detailed modeling or predictions. Nevertheless, current evidence suggests that at least Titania and Oberon might have anomalously high densities of 2-39 cm(-3), possibly requiring almost ice-free hydrated silicates or formation in a CO-rich environment, implying presence of CO-clathrate and a small ice/rock ratio. Trition and the four largest satellites of Uranus are massive enough to have undergone significant accretional heating and early differentiation; NH3-H2O volcanism; partial outgassing of CO, N2, Ch4; formation of dark surficial deposits of carbon-rich material obtained by UV irradiation of outgassed material; and, at least in the cases of Ariel and Triton, a possibility of weak ongoing icy volcanic activity. Triton may be the largest captured body in the solar system, with an unusual history and composition, including the possibility of substantial liquid or solid nitrogen obtained from either primordial NH3 photolysis or clathrate decomposition.

Stevenson, D. J.↗

Characteristics of wavelike fluctuations in Dynamics Explorer neutral composition data

Wavelike fluctuations in neutral composition data obtained with the neutral atmospheric composition system quadrupole mass spectrometer carried aboard the Dynamics Explorer (DE 2) satellite are at a maximum in the vicinity of the magnetic poles. Typical rms amplitudes near the poles for N2, O, He, and Ar fluctuations in the 400- to 4000-km-wavelength band are found to be 11, 6, 6, and 20 percent, respectively. Amplitudes near the equator are roughly a third of the polar amplitudes, and activity in the 50- to 400-km-wavlength band is roughly 20 percent of the longer-wavelength activity.

Hedin, A. E.↗

Mechanistic studies of the CO-oxidation reaction on catalysts for use in long-life CO2 lasers

The catalytic recombination of carbon monoxide and oxygen was studied under conditions expected to be present in a sealed E-beam CO2 laser system. These conditions are typically a gas inlet temperature of 60 C, a substoichiometric CO/O2 ratio of ca. 2.5/1 with an oxygen feed rate of ca. 5 micromoles/s, a carrier gas comprising He, N2 and CO2 in the ratio of 3:2:1, near atmospheric pressure and a gas velocity of 4 m/s. Heterogeneous catalysts, based on precious metal supported on tin oxide, have been coated onto ceramic monoliths and tested for catalytic activity and stability after a reduction/passivation step. Two catalyst systems have been chosen. These are Pt/Pd/SnO2 and Pt/Ru/SnO2. Under the conditions described above, a characteristic decline in catalytic activity is apparent for both systems, and exit gas temperature has been recognized as a sensitive parameter by which to monitor the activity changes. A semilogarithmic plot of exit temperature as a function of time has revealed two distinct processes connected with the decline in activity: one process is associated with reduction of the oxidized precious metal (at Site A), whilst the other is related to the formation and approach to steady-state of an active site at the metal/support interface (Site B).

Dawood, Talat↗

Oxygen supersaturation in ice-covered Antarctic lakes - Biological versus physical contributions

Lake Hoare is one of a number of ice-covered polar lakes in the Dry Valley Region of southern Victoria Land, Antarctica. Analysis of N2, O2, and Ar in bubbles from this lake's ice indicates that while O2 is about 2.4 times supersaturated in the water below the ice, only 11 percent of the O2 input to this lake is due to biological activity and the balance is derived from meltwater inflow. In Lake Hoare, as much as 70 percent of total gas loss may occur by advection through the ice cover; the remaining gas fractions are removed by respiration at the lower boundary in the case of O2, and by molecular exchange with the atmosphere in the peripheral summer moat around the ice.

Craig, H.↗

The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems

The bond dissociation energies (D sub e) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of D sub e with respect to the one particle basis is studied at the single reference modified coupled-pair functional (MCPF) level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration interaction (MRCI) D sub e values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size extensive averaged coupled pair functional (ACPF) method. It was found that the full valence complete active space self consistent field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds. To achieve chemical accuracy (1 kcal/mole) for the D sub e values of the doubly bonded species C2H4 and N2H2 requires one particle basis sets including up through h angular momentum functions (l = 5) and a multireference treatment of electron correlation: still higher levels of calculation are required to achieve chemical accuracy for the triply bonded species C2H2 and N2.

Langhoff, Stephen R.↗

N2-to-NH3 conversion by excess electrons trapped in point vacancies on 5f-element dioxide surfaces

Ammonia (NH 3 ) is one of the basic chemicals in artificial fertilizers and a promising carbon-free energy storage carrier. Its industrial synthesis is typically realized via the Haber−Bosch process using traditional iron-based catalysts. Developing advanced catalysts that can reduce the N 2 activation barrier and make NH 3 synthesis more efficient is a long-term goal in the field. Most heterogeneous catalysts for N 2 -to-NH 3 conversion are multicomponent systems with singly dispersed metal clusters on supporting materials to activate N 2 and H 2 molecules. Herein, we report single-component heterogeneous catalysts based on 5 f actinide dioxide surfaces (ThO 2 and UO 2 ) with oxygen vacancies for N 2 -to-NH 3 conversion. The reaction cycle we propose is enabled by a dual-site mechanism, where N 2 and H 2 can be activated at different vacancy sites on the same surface; NH 3 is subsequently formed by H − migration on the surface via associative pathways. Oxygen vacancies recover to their initial states after the release of two molecules of NH 3 , making it possible for the catalytic cycle to continue. Our work demonstrates the catalytic activities of oxygen vacancies on 5 f actinide dioxide surfaces for N 2 activation, which may inspire the search for highly efficient, single-component catalysts that are easy to synthesize and control for NH 3 conversion.

36 MATERIALS SCIENCE↗