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A microscopic description of the pressure dependence of intramolecular vibrational modes in simple molecular crystals has been formulated using a classical perturbation theory. Quantitative agreement with experiment is demonstrated and it is shown that frequency changes at phase transitions are large enough to be observed optically.
Differential Absorption Lidar (DIAL) measurements in the A-band of molecular oxygen were suggested as a means of profiling atmospheric density. Progress towards this capability is reported.
Ozone was produced by UV photolysis (157-200 nm) of molecular oxygen. The product ozone is enriched in O-17 and O-18 on a mass-independent basis, similar to the fractionations observed in an electrical discharge. The magnitude of O-18 and O-17 enrichment decreases with decreasing pressure, suggesting the presence of two fractionation mechanisms with differing delta-O-17/delta-O-18 ratios. One of the end members would be mass-independent with delta-O-18 equal to delta-O-17 equal to about 90 percent, which is dominant above about 20 torr. The second process which is significant below about 6 torr produces O3 with delta-O-18 equals about -55 percent, delta-O-17 equals about -27.5, possibly due to isotopic selectivity in diffusion to the reaction systems wall. The delta-O-17 = delta-O-18 isotopic fractionation resembles that observed in stratospheric ozone, though the magnitude of fractionation is a factor of four less.
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Ignition delay times for stoichiometric hydrogen-oxygen in argon with and without carbon dioxide were measured behind reflected shock waves. A 20-reaction kinetic mechanism models the measured hydrogen-oxygen delay times over the temperature range 950 to 1300 K. The chaperon efficiency for carbon dioxide determined for the hydrogen-oxygen carbon dioxide mixture was 7.0. This value is in agreement with literature values but much less than a recent value obtained from flow tube experiments. Delay times measured behind a reflected shock wave were about 20% longer than those measured behind incident shock waves. The kinetic mechanism successfully modeled the high-pressure data of Skinner and the hydrogen-air data of Stack. It is suggested that the lowest temperature points for the hydrogen-air data of Slack are unreliable and that the 0.27-atm data may illustrate a case where vibrational relaxation of nitrogen is important. The reaction pathway HO2 yields H2O2 yields OH yields H was required to model the high-pressure data of Skinner. The successful modeling of the stoichiometric hydrogen-air data demonstrates the appropriateness of deriving kinetic models from data for gas mixtures highly diluted with argon. The technique of reducing a detailed kinetic mechanism to only the important reactions for a limited range of experimental data may render the mechanism useless for other test conditions.
An investigation was performed of the technical steps required to design a solar powered oxygen-iodine laser. Singlet delta oxygen is formed upon transfer of energy from selected photoexcited dye molecules to ground state molecular oxygen and then is concentrated and stored as an endoperoxide by reaction with an aromatic hydrocarbon. The endoperoxide, when heated, releases singlet oxygen in high yield thus providing a regenerable source of laser fuel. Energy transfer from dye molecules to molecular oxygen was investigated. When dye molecules were adsorbed to polymer substrates it was observed that the dye became embedded in the polymer matrix. Porphin dyes were incorporated into films of 1,4-dimethyl-2-poly(vinylnaphthalene), 2PVN. An endoperoxide was formed when porphin-doped 2PVN was exposed to visible radiation. This demonstrates the possibility of generating singlet oxygen using solar energy and concentrating and storing it in one simple step. Transport of energy by exciton migration in polycrystalline dye films was also investigated.
A new variety of low resolution spectrometer is described. This device, an image plane detector spectrophotometer, has high sensitivity and modest resolution sufficient to determine the rotational temperature and brightness of molecular band emissions. It uses an interference filter as a dispersive element and a multichannel image plane detector as the photon collecting device. The data analysis technqiue used to recover the temperature of the emitter and the emission brightness is presented. The atmospheric band of molecular oxygen is used to illustrate the use of the device.
An investigation is reported of the use of laser-induced fluorescence on oxygen for the measurement of air temperature and its fluctuations owing to turbulence in hypersonic wind tunnel flows. The results show that for temperatures higher than 60 K and densities higher than 0.01 amagat, the uncertainty in the temperature measurement can be less than 2 percent if it is limited by photon-statistical noise. The measurement is unaffected by collisional quenching and, if the laser fluence is kept below 1.5 J/sq cm, it is also unaffected by nonlinear effects which are associated with depletion of the absorbing states.
This paper investigates the statistical retrieval of cell top altitude using high-resolution passive 118-GHz multichannel precipitation cell imagery. The observations were made using the millimeter-wave temperature sounder scanning spectrometer aboard the NASA ER-2 high-altitude research aircraft, during the Genesis of Atlantic Lows Experiment and the Cooperative Huntsville Meteorological Experiment, 1986. Results obtained using a nonlinear statistical 118-GHz cell top altitude retrieval technique are presented, illustrating a systematic method for parameter estimation from noisy nonlinearly dependent observations.
Laser-induced fluorescence in oxygen, in combination with Raman scattering, is shown to be an accurate means by which temperature, density, and their fluctuations due to turbulence can be measured in air flows associated with high-speed wind tunnels. For temperatures above 60 K and densities above 0.01 amagat, the uncertainty in the temperature and density measurements can be less than 2 and 3 percent, respectively, if the signal uncertainties are dominated by photon-statistical noise. The measurements are unaffected by collisional quenching and can be achieved with laser fluences for which nonlinear effects are insignificant. Temperature measurements using laser-induced fluorescence alone have been demonstrated at known densities in the range of low temperatures and densities which are expected in a hypersonic wind tunnel.
A nonlinear least-squares method of retrieving predissociation linewidths from the experimental absolute absorption cross sections of Yoshino et al. (1983) has been applied to the (1,0)-(12,0) Schumann-Runge bands of oxygen. The predissociation linewidths deduced are larger than the theoretical predictions of Julienne (1976) and the latest measurements of Lewis et al. (1986). The larger linewidths found will have an impact on calculations of solar flux penetration into the earth atmosphere and of the photodissociation rates of trace species in the upper atmosphere.
Radiometric observations at 118 GHz are compared to a planar-stratified numerical radiative transfer model, in order to study the microwave scattering and emission properties of precipitation cells. Agreement between observed and computed brightness perturbations is shown to be within 10 percent over the radiometrically opaque, mature regions of the cell. Transparent-channel cell top reflectivities of up to 50 percent in the convective core region and 6 percent in the anvil region are determined, using perturbed and nonscattering weighting functions. A parameterized rain cell model is used in a content analysis of 118 GHz precipitation cell spectra. The dominant 118-GHz spectral modes are found to contain useful data on the cell top altitude; they are applicable for detection of transparent anvil regions.
Report describes computations of unsteady facilitated transport of oxygen through liquid membrane of hemoglobin. Used here, "facilitated transport" means diffusion of permeant through membrane in which that diffusion enhanced by reversible chemical reaction between permeant and membrane. In this case, reversible reactions between hemoglobin and oxygen.
Direct extraction and reaction of the 50 ppm H found in mature lunar soil with a small fraction of the 1 percent ilmenite found in even the most Ti-poor lunar soils is a viable method of producing H2O2 and H2O for propellants and life support. A plant with a mass of approximately 62 metric tons can produce about 8 metric tons of LOX and 1.2 metric tons of LH2 per month. The concept is viable in even Ti-poor regions if the soils have long exposure to solar wind. The plant processes over 29,000 tons of soil with about 50 ppm H per month. The mine that feeds the plant excavates over 8600 sq m per month with a fleet of three front-end loaders and five haulers. Trade studies demonstrate that nuclear power accompanied by a high process plant duty cycle results in a far smaller installation than a solar-powered unit.
Laser-induced fluorescence in oxygen, in combination with Raman scattering, is shown to be an accurate means by which temperature, density, and their fluctuations owing to turbulence can be measured in air flows associated with high-speed wind tunnels. For temperatures above 60 K and densities above 0.01 amagat, the uncertainties in the temperature and density measurements can be less than 2 percent, if the signal uncertainties are dominated by photon statistical noise. The measurements are unaffected by collisional quenching and can be achieved with laser fluences for which nonlinear effects are insignificant. Temperature measurements using laser-induced fluorescence alone have been demonstrated at known densities in the range of low temperatures and densities which are expected in a hypersonic wind tunnel.
A fast and nonintrusive velocity and temperature diagnostic based on oxygen absorption is presented. The system uses a GaAlAs tunable diode laser, ramped and modulated in wavelength at high frequency. Detection is performed at twice the modulating frequency, leading to second harmonic absorption lineshapes. Velocity is inferred from the wavelength shift of the absorption line center due to the Doppler effect. Temperature is determined by comparing experimental and calculated lineshapes. Capabilities of the technique for studies of transient high-speed flows are demonstrated in shock tube experiments. Good agreement is obtained with predicted temperatures and velocities when pressure-induced shifts are accounted for.
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Electrochemical system includes fuel cells that convert high-energy-density chemical propellants to atmospheric gases. System provides cooling, water, and electrical energy. Applicable to terrestrial enclosed environments, laboratories, chemical processing plants, or portable medical facilities.