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At least 91 records · Page 5

Effects of low concentrations of O2 and CO on the ion-clustering reactions in the lower ionosphere of Mars

It is demonstrated that under conditions which approximate those of the Martian ionosphere traces of CO and O2 can be effectively incorporated in ion clusters via ion-molecule reaction schemes initiated by the CO2(+) ion. For example, when 0.3% CO is added to CO2, (CO)2(+), and /(CO)2CO2/(+) appear as the major cations (584 A radiation, 300 K). In mixtures containing O2 in addition to CO, (CO2,O2+) and /(CO2)2O2/(+) are important species. A recently proposed mechanism to account for the low abundance of CO and O2 in the Martian atmosphere is discussed in the light of these observations.

Sieck, L. W.↗

Formation of HO2/+/ by reaction of metastable O2/+/ ions with H2

The photoionization efficiency curves of H2(+), O2(+), and HO2(+) have been studied in a mixture of hydrogen and oxygen over the wavelength range from 650 to 810 A. The HO2(+) ion appears at 804 A, the threshold for ionization of H2, by the reaction H2(+) + O2 yields HO2(+) + H. The relative photoionization efficiency curves of H2(+) and HO2(+) are the same from 804 to 764 A. Below 764 A production of the 4 Pi u metastable electronic state of O2(+) leads to the formation of HO2(+) by the reaction O2(+)(a 4 Pi u) + H2 yields HO2(+) + H.

Ajello, J. M.↗

Proton transfer reactions from H3/+/ ions to N2, O2, and CO molecules

The rate constants for proton transfer from H3(+) ions to N2, O2, and CO have been measured as function of hydrogen-buffer-gas partial pressure. The rate constant for proton transfer from H3(+) to N2 shows a very large pressure dependence, increasing from 1.0 by 10 to the -9th power cu cm/s at low H2 partial pressures to 1.7 by 10 to the -9th power cu cm/s at high H2 partial pressures. The rate constants for proton transfer from H3(+) to O2 and CO are constant with partial pressure of H2. The roles of excess vibrational energy in H3(+) ions and of equilibrium between forward and back reactions are discussed. Back reaction is observed only for the reaction of H3(+) ions with O2, and an equilibrium constant of 2.0 (plus or minus 0.4) at 298 K has been determined. From these data, the proton affinity of O2 is deduced to be 0.47 (plus or minus 0.11) kcal/mole higher than that of H2.

Kim, J. K.↗

A photoionization study of the formation of NO2/+/ by reaction of excited O2/+/ ions with NO

Photoionization mass spectrometer results are presented for the first observation of the ion-molecule reaction in which O2(+) + NO yields NO2(+) + O. The reaction is energetically possible for ground state O2(+) ions in the lowest vibrational level. Photoionization efficiency curves for NO(+), O2(+), and NO2(+) are presented and compared, with special emphasis on autoionization features. In addition to the production of NO2(+) by the cited reaction, there is also a possibility for NO2(+) formation by the process O2 + NO(+) yielding NO2(+) + O. This reaction is calculated to be exothermic for incident photon energies of 11.73 eV.

Ajello, J. M.↗

Interstellar O2. I - Abundance, excitation, and prospects for detection of O-16O-18 at radio frequencies

Molecular oxygen, O2, is predicted to be an important constituent of the interstellar gas, but it has not yet been detected in interstellar clouds. In this paper, the gas phase production and destruction of O2 are reconsidered, a non-LTE calculation of level populations at cloud temperatures is presented, and O2 column densities in diffuse and dark clouds are predicted. Ground-based detection of the 234 GHz line of O-16O-18 is shown to be feasible; if CO and O2 are comparable in abundance in clouds similar to the Taurus molecular cloud or in giant molecular clouds, the brightness temperature is predicted to be 0.1 K.

Black, J. H.↗

Prediction of structures and magnetic orientations in solid alpha and beta-O2

A quasi-harmonic-lattice-dynamics method coupled with a pattern-recognition optimization scheme is used to determine the minimum energy structures and magnetic orientations of solid oxygen. It is shown that the magnetic interaction is responsible for the stability of alpha-O2 with respect to beta-O2 at zero temperature and pressure. The calculated alpha-O2 lattice parameters, magnetic orientations, and sublimation energy are in good agreement with experiment. Phonon dispersion curves are calculated at vector k not equal to zero and the acoustic sound velocities are determined. The rms translational and orientational fluctuations from equilibrium are also calculated. The beta-O2 phase is described by constraining the magnetic moments so that the magnetic Hamiltonian preserves the hexagonal symmetry of the crystal. The calculated lattice parameters are in good agreement with the experiments, and a three-sublattice, quasi-helical magnetic orientation is predicted from structural and energetic considerations.

Etters, R. D.↗

Sensitivity of N2O, CFCl3, and CF2Cl2 two-dimensional distributions to O2 absorption cross sections

A good test of the transport and ultraviolet radiation treatment for any model can be based on the consideration of the three gases N2O, CFCl3 (F-11), and CF2Cl2 (F-12). Attention is given to a two-dimensional model which makes it possible to study changes in seasonal and latitudinal distributions which result from O2 cross-section changes. A latitude-dependent ozone decrease has already been predicted by two-dimensional models for chlorofluoromethane (CFM) release. For this reason, it is of interest to determine if a strong latitude-dependent change is detectable in the CFM profiles. One-dimensional models have pointed toward a trend of decreased trace gas concentrations in correlation with decreased O2 cross sections. The O2 cross sections between 180 and 230 nm are changed within a range of experimentlly allowed values. It is found that lower O2 absorption cross sections lead to larger photodissociation rates for the trace gases F-11, F-12, and N2O.

Jackman, C. H.↗

The O2 atmospheric 0-0 band and related emissions at night from Spacelab 1

A comparison of theoretically determined and measured O2 atmospheric (0-0) band intensities is presented. In view of suggestions that the O2 atmospheric emission and the atomic oxygen O(1S) emission both arise from the same intermediate state of O2, the measured 5577 A emission is also compared with theory; a similar comparison is made for the Herzberg bands of O2. It is concluded that the theories explaining these emissions do not yet provide a consistent picture.

Torr, M. R.↗

Dissociation of metastable O2 as a potential source of atmospheric odd oxygen

An analysis of the possible dissociation of metastable oxygen molecules subject ot constraints imposed by selection rules for molecular transitions, airglow observations, and atmospheric chemistry leads to the following conclusions. Dissociation of O2(b1Sigma g +) must produce a negligible number of oxygen atoms at all altitudes in the earth's atmosphere. However, if the dissociation cross section of O2(a1Delta g) has a maximum value in the range 10 to the -20th to 10 to the -19th/sq cm, then the process O2(a1Delta g) + h(nu) yields O2(C3Delta u) yields O(3P) + O(3P) will constitute a significant, and potentially the major, source of odd oxygen in the uppermost stratosphere and mesosphere.

Frederick, J. E.↗

Vibrational excitation in O2(B1Sigma g+)

Excitation processes for O2(b1Sigma g+) in aurorae, in the nightglow, and in laboratory sources are discussed. It is shown that the observed vibrational distribution in aurorae is consistent with the O2(+) + NO charge-transfer mechanism. Arguments are presented for the case the quenching of O2(b) in vibrational levels above v-prime = 1 is rapid, and that therefore the auroral source is much larger than previously supposed. It is suggested that oxygen atoms are an efficient quencher for O2(b) levels above v-prime = 1.

Slanger, Tom G.↗

A study of Na(x)Pt3O4 as an O2 electrode bifunctional electrocatalyst

The present study suggests that polytetrafluoroethylene (PTFE) bonded Na(X)Pt3O4 gas porous diffusion electrodes may be a viable candidate for bifunctional O2 reduction and evolution activity. The electrodes exhibited Tafel slopes of about 0.06 V/decade for both O2 reduction an evolution. For O2 reduction, the 0.06 slope doubled to 0.12 V/decade at larger current densities. Preliminary stability testing at 24 C suggest that the Na(x)Pt3O4 electrodes were relatively stable at reducing and oxidizing potentials typically encountered at the O2 electrodes in a regenerative fuel cell.

Fielder, William L.↗

Measurements of KrF laser-induced O2 fluorescence in high-temperature atmospheric air

Conditions for obtaining laser-induced O2 fluorescence using a tunable KrF laser has been determined theoretically and experimentally. With this laser source, O2 rotational temperature measurement is possible even in the absence of vibrational equilibrium. Temperature measurement using a two-line excitation scheme has been demonstrated in a high-temperature atmospheric-air furnace. A measurement uncertainty of 10.7 percent for the temperature range 1325-1725 K was realized. At atmospheric pressure, O2 LIF measurements are possible for air temperatures above 1250 K. Interference from OH fluorescence in reacting flows can be avoided by the proper selection of O2 transitions. Depletion of the ground state population by the incident laser is negligible for intensities below 7.5 x 10 to the 6th W/sq cm/per cm.

Grinstead, Jay H.↗

Electrochemical CO2 and O2 separation for crew and plant environments

The study describes a closed ecosystem concept that includes electrochemical CO2 and O2 separators and a moisture condenser/separator for maintaining CO2, O2, and humidity levels in the crew and plant habitats at their respective optimal conditions. The key processes of this concept are aqueous electrolyte-based electrochemical CO2 and O2 separations. The principles and cell characteristics of these electrochemical gas separation processes are described. Also presented are descriptions of test hardware and the test results of the Electrochemical CO2 Separator (ECS) and the Electrochemical O2 Separator (EOS), and the combination of the ECS and the EOS. The test results proved that the ECS and EOS processes for the combined concept are viable.

Lee, M. G.↗

An evaluation of the rate of absorption of solar radiation in the O2(X3Sigma-g - b1Sigma-g) transition

The rate at which molecular oxygen absorbs radiation in the O2(X3Sigma-g - b1Sigma-g) transition is calculated using a line-by-line radiative transfer model. This rate is critical to the determination of the population of the O2(b1Sigma-g) state required for studies of the O2(b1Sigma-g - X3Sigma-g) dayglow, the O2(a1Delta-g - X3Sigma-g) dayglow, and possibly the rates of oxidation of H2 and N2O. Previous evaluations of this rate (which is sometimes called the g-factor) have significantly overestimated its value. The rate is tabulated as a function of altitude, pressure, and solar zenith angle.

Mlynczak, Martin G.↗

Continuous Remote Measurements of Atmospheric O2 Concentrations in Relation to Interannual Variations in Biological Production and Carbon Cycling in the Oceans

We successfully initiated a program to obtain continuous time series of atmospheric O2 concentrations at a semi-remote coastal site, in Trinidad, California. The installation, which was completed in September 1999, consists of a commercially-available O2 and CO2 analyzers interfaced to a custom gas handling system and housed in a dedicated building at the Trinidad site. Ultimately, the data from this site are expected to provide constraints, complementing satellite data, on variations in ocean productivity and carbon exchange on annual and interannual time scales, in the context of human-induced changes in global climate and other perturbations. The existing time-series, of limited duration, have been used in support of studies of the O2/CO2 exchange from a wild fire (which fortuitously occurred nearby in October 1999) and to quantify air-sea N2O and O2 exchanges related to coastal upwelling events. More generally, the project demonstrates the feasibility of obtaining semi-continuous O2 time series at moderate cost from strategic locations globally.

Keeling, Ralph F.↗

Kinetic Studies of Iron Deposition Catalyzed by Recombinant Human Liver Heavy, and Light Ferritins and Azotobacter Vinelandii Bacterioferritin Using O2 and H2O2 as Oxidants

The discrepancy between predicted and measured H2O2 formation during iron deposition with recombinant heavy human liver ferritin (rHF) was attributed to reaction with the iron protein complex [Biochemistry 40 (2001) 10832-10838]. This proposal was examined by stopped-flow kinetic studies and analysis for H2O2 production using (1) rHF, and Azotobacter vinelandii bacterial ferritin (AvBF), each containing 24 identical subunits with ferroxidase centers; (2) site-altered rHF mutants with functional and dysfunctional ferroxidase centers; and (3) rccombinant human liver light ferritin (rLF), containing 110 ferroxidase center. For rHF, nearly identical pseudo-first-order rate constants of 0.18 per second at pH 7.5 were measured for Fe(2+) oxidation by both O2 and H2O2, but for rLF, the rate with O2 was 200-fold slower than that for H2O2 (k-0.22 per second). A Fe(2+)/O2 stoichiometry near 2.4 was measured for rHF and its site altered forms, suggesting formation of H2O2. Direct measurements revealed no H2O2 free in solution 0.5-10 min after all Fe(2+) was oxidized at pH 6.5 or 7.5. These results are consistent with initial H2O2 formation, which rapidly reacts in a secondary reaction with unidentified solution components. Using measured rate constants for rHF, simulations showed that steady-state H2O2 concentrations peaked at 14 pM at approx. 600 ms and decreased to zero at 10-30 s. rLF did not produce measurable H2O2 but apparently conducted the secondary reaction with H2O2. Fe(2+)/O2 values of 4.0 were measured for AvBF. Stopped-flow measurements with AvBF showed that both H2O2 and O2 react at the same rate (k=0.34 per second), that is faster than the reactions with rHF. Simulations suggest that AvBF reduces O2 directly to H2O without intermediate H2O2 formation.

Bunker, Jared↗

Mechanisms of O2 Sputtering from Water Ice by keV Ions

We have conducted experiments on the sputtering of water ice by 100 keV Ar(+) between 20 and 150 K. Our findings indicate that the temperature dependence of the total sputtering yield is heavily influenced by the thermal and irradiation history of the ice, showing a complex dependence on irradiation fluence that is correlated to the ejection of O2 molecules. The results suggest that O2 produced by the ions inside the ice diffuses to the surface where it is trapped and then ejected via sputtering or thermal desorption. A high concentration of O2 can trap in a subsurface layer during bombardment at 130 K, which we relate to the formation of hydrogen and its escape from that region. A simple model allows us to determine the depth profile of the absolute concentration of O2 trapped in the ice.

Teolis, B. D.↗

Results of a 3-day Pilot Study to Validate Planetary Prebreathe Protocols Using a 56.5 kPa 34% O2, 66% N2 Saturation Cabin Atmosphere

INTRODUCTION: Apollo missions used 100% O2 cabin atmospheres which effectively eliminated the risk of decompression sickness (DCS) during extravehicular activities (EVAs, ‘spacewalks’); however, this atmosphere presented a flammability risk that is no longer acceptable to NASA. Denitrogenation prebreathe protocols used to mitigate DCS risk for Space Shuttle and International Space Station EVAs are validated for the microgravity environment, but the significantly increased risk of DCS during equivalent ambulatory surface EVAs make these protocols inapplicable to planetary/Lunar missions. An “exploration atmosphere” of 56.5 kPa (8.2 psia), 34% O2, 66% N2 has been recommended by NASA for future Moon and Mars missions as a compromise that balances subsequent pre-EVA prebreathe duration, hypoxia, and flammability risk, assuming a 29.6 kPa (4.3 psi) spacesuit. Prebreathe validation studies was initiated utilizing a three-story 6m diameter hypobaric chamber at NASA’s Johnson Space Center. Here, we report the results of a 3-day human-in-the-loop system checkout. METHODS: Six volunteers acclimated to the 56.6kPa/34% O2 66% N2 environment for 48hrs prior to conducting a 20-minute prebreathe and a 6-hour simulated EVA at 34kPa/85% O2 / 15% N2. The EVA simulation was designed to include tasks that are physically and ergonomically representative of future planetary EVAs. Decompression stress was evaluated by serial doppler and echocardiographs, as well as by clinical features of DCS signs/symptoms. RESULTS AND DISCUSSION: Preliminary data analysis noted venous gas emboli (VGE) in 3 of 6 subjects, with peak Grade II VGE by Doppler and peak E-B score of 5 by cardiac ultrasonography. No volunteers were diagnosed with DCS during this initial test. No acute hypoxic symptoms were noted. Musculoskeletal and gastrointestinal complaints were noted, likely associated with the exercise load and the food system. Validation of exploration prebreathe protocols has since been initiated with an 11-day saturation test using the same facility and protocol.

Alejandro Garbino↗