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Charge exchange of metastable 2D oxygen ions with molecular oxygen - A new source of thermospheric O2/+/ ions

Reactions involving metastable ions are difficult to study in the laboratory. Much new information on these reactions has been derived from satellite measurements of aeronomic parameters. In this paper, Atmosphere Explorer D data are used to study charge exchange of metastable O(+)(2D) ions with O2. Using direct measurements of the O2 at 200 km to compute O2 densities at 300 km and supporting ionic concentrations and temperature observations, we find the rate coefficient for this reaction to be 1 + or - 0.6 times 10 to the minus 9th cu cm/sec. The process constitutes a significant source of O2(+) ions in the F2 layer at times when the N2 and O2 densities are enhanced. This finding leads to the conclusion that charge exchange with O2 must be a major sink for O(+)(2D) and an important source of O2(+) ions in the E region, because of the increase in the O2 concentration/N2 concentration ratio with decreasing altitude. The results imply that 80% of all O(+) ions formed in the E region are converted to O2(+) and that only about 20% of the metastable O(+) ions are converted into N2(+) through charge exchange with N2.

Torr, D. G.↗

The Change in Oceanic O2 Inventory Associated with Recent Global Warming

Oceans general circulation models predict that global warming may cause a decrease in the oceanic O2 inventory and an associated O2 outgassing. An independent argument is presented here in support of this prediction based on observational evidence of the ocean's biogeochemical response to natural warming. On time scales from seasonal to centennial, natural O2 flux/heat flux ratios are shown to occur in a range of 2 to 10 nmol O2 per Joule of warming, with larger ratios typically occurring at higher latitudes and over longer time scales. The ratios are several times larger than would be expected solely from the effect of heating on the O2 solubility, indicating that most of the O2 exchange is biologically mediated through links between heating and stratification. The change in oceanic O2 inventory through the 1990's is estimated to be 0.3 - 0.4 x 10(exp 14) mol O2 per year based on scaling the observed anomalous long-term ocean warming by natural O2 flux/heating ratios and allowing for uncertainty due to decadal variability. Implications are discussed for carbon budgets based on observed changes in atmospheric O2/N2 ratio and based on observed changes in ocean dissolved inorganic carbon.

Keeling, Ralph↗

Fiber-Optic Determination of N2, O2, and Fuel Vapor in the Ullage of Liquid-Fuel Tanks

A fiber-optic sensor system has been developed that can remotely measure the concentration of molecular oxygen (O2), nitrogen (N2), hydrocarbon vapor, and other gases (CO2, CO, H2O, chlorofluorocarbons, etc.) in the ullage of a liquid-fuel tank. The system provides an accurate and quantitative identification of the above gases with an accuracy of better than 1 percent by volume (for O2 or N2) in real-time (5 seconds). In an effort to prevent aircraft fuel tank fires or explosions similar to the tragic TWA Flight 800 explosion in 1996, OBIGGS are currently being developed for large commercial aircraft to prevent dangerous conditions from forming inside fuel tanks by providing an inerting gas blanket that is low in oxygen, thus preventing the ignition of the fuel/air mixture in the ullage. OBIGGS have been used in military aircraft for many years and are now standard equipment on some newer large commercial aircraft (such as the Boeing 787). Currently, OBIGGS are being developed for retrofitting to existing commercial aircraft fleets in response to pending mandates from the FAA. Most OBIGGS use an air separation module (ASM) that separates O2 from N2 to make nitrogen-enriched air from compressed air flow diverted from the engine (bleed air). Current OBIGGS systems do not have a closed-loop feedback control, in part, due to the lack of suitable process sensors that can reliably measure N2 or O2 and at the same time, do not constitute an inherent source of ignition. Thus, current OBIGGS operate with a high factor-of-safety dictated by process protocol to ensure adequate fuel-tank inerting. This approach is inherently inefficient as it consumes more engine bleed air than is necessary compared to a closed-loop controlled approach. The reduction of bleed air usage is important as it reduces fuel consumption, which translates to both increased flight range and lower operational costs. Numerous approaches to developing OBIGGS feedback-control sensors have been under development by many research groups and companies. However, the direct measurement of nitrogen (N2) is a challenge to most OBIGGS ullage sensors (such as tunable diode laser absorption) as they cannot measure N2 directly but depend on the measurement of oxygen (O2). The problem with a singular measure of O2, is that as the concentration (number density) of O2 decreases due to the inerting process or due to lower pressures from high altitudes, the precision and accuracy of the O2 measurement decreases. However, measuring O2 density in combination with N2 density (which is more abundant in air and in a N2-inerted fuel tank) can provide a much more accurate and reliable determination of the OBIGGS efficacy.

Nguyen, Quang-Viet↗

Modeling Electrolytic O2 Recovery from Metabolic CO2 for Advanced Closed Loop Life Support Systems in Extraterrestrial Human Missions

The International Space Station (ISS) is currently equipped with a complex, heavy, and power consuming system that recovers approximately 50% of O2 from metabolic CO2. Future long duration human missions to the Moon and Mars will necessitate a sustainable and highly efficient metabolic oxygen recovery system capable of yielding a minimum of 75% O2 recovery. A Macrofluidic Electrochemical Reactor (MFECR) technology development effort is currently underway at NASA Marshall Space Flight Center (MSFC) to significantly increase current metabolic O2 recovery efficiency, expand mission sustainability, and reduce complexity of the system. The novel design combines CO2 conversion to O2 along with C2H4 as byproduct and water electrolysis (currently conducted in two separate units) into a single compact unit that runs at standard conditions and is theoretically capable of generating O2 with a theoretical maximum metabolic CO2 conversion of 73% while consuming less than metabolic water. This paper presents a comprehensive multi-physic 3D model developed at MSFC on CO2 conversion to O2 and C2H4 at standard conditions via MFECR. The 3D spatial domain of the model is a replica of the actual MFECR’s 3D drawing generated for the MFECR fabrication and operated to recover O2 from CO2 yielding C2H4 as byproduct. Electrochemical (EC) physics that includes EC multicomponent reaction mechanisms, mass transport, and electrical current density distributions is coupled in the model with all the other physics phenomena involved in the MFECR’s process, such as two-phase flow, free and porous fluid regimes, multicomponent mass transfer, heat transfer, and DC electrical current generation along with Joule heating effect. The EC reaction sections of the MFECR consists of two porous gas diffusion electrodes (GDE) and an electrolyte serpentine channel sandwiched in the middle. The CO2 feeds the cathode serpentine channel and part of the O2 product is fed back to the anode serpentine chamber. An alkaline solution feeds the electrolyte serpentine chamber wetting the GDEs of both, the anode and cathode allowing the OH- ionic transport between them. The EC reactions in the cathode’s GDE yield C2H4 from CO2 and H2 from water while the EC reaction in the anode’s GDE yields O2. The authors will present in this paper the validation of the model using experimental data and the utilization of the validated model in building a reliable simulator that will not only assist the authors on the MFECR design but also the optimization of its operation in the ISS and future spatial human missions.

Jesus A Dominguez↗

CO2-O2 Interactions in Extension of Tolerance to Acute Hypoxia

Advantageous and/or detrimental influences associated with purposeful deviations from atmospheric levels of O2 and CO2 are studied. Specific goals have been directed to simulating situations of emergency or accidental exposure to hypoxic (10% O2) environments. They included establishing dynamic effects of hypoxia with and without CO2 (rate of acute adaptation), and stable-state (equilibrium) effects on blood and brain oxygenation. They also included effects on the physiological parameters of respiration and blood gas composition which underlie brain oxygenation. For 10% O2, a complete experiment consisted of three identical rest-exercise phases of 32 minutes duration. Following a five minute air control period, each inspired gas was administered over the next 27 minutes. The test gases were room air control, 10% +/- 0.1% O2 with 4% +/- 0.1% CO2, and 10% +/- 0.1% O2. A minimum of 45 minutes separated each phase. Relative to inspiration of 10% O2, brain oxygenation is enhanced by addition of 4% CO2. This is accomplished by increasing the rate at which O2 in arterial blood is supplied to the brain circulation (well above even the normoxic level), and on relative improvement in the arterial pressure of O2.

Lambertsen, C. J.↗

The 2140 cm-1 (4.673 microns) solid CO band: the case for interstellar O2 and N2 and the photochemistry of nonpolar interstellar ice analogs

The infrared spectra of CO frozen in nonpolar ices containing N2, CO2, O2, and H2O and the UV photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140 cm-1 (4.673 microns) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing nonpolar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices. The N2 and O2 absorptions at 2328 cm-1 (4.296 microns) and 1549 cm-1 (6.456 microns), respectively, are also shown. The best matches between the narrow interstellar band and the feature in the laboratory spectra of nonpolar ices are for samples which contain comparable amounts of N2, O2, CO2, and CO. Co-adding the CO band from an N2:O2:CO2:CO = 1:5:1/2:1 ice with that of an H2O:CO = 20:1 ice provides an excellent fit across the entire interstellar CO feature. The four-component, nonpolar ice accounts for the narrow 2140 cm-1 portion of the feature which is associated with quiescent regions of dense molecular clouds. Using this mixture, and applying the most recent cosmic abundance values, we derive that between 15% and 70% of the available interstellar N is in the form of frozen N2 along several lines of sight toward background stars. This is reduced to a range of 1%-30% for embedded objects with lines of sight more dominated by warmer grains. The cosmic abundance of O tied up in frozen O2 lies in the 10%-45% range toward background sources, and it is between 1% and 20% toward embedded objects. The amount of oxygen tied up in CO and CO2 frozen in nonpolar ices can be as much as 2%-10% toward background sources and on the order of 0.2%-5% for embedded objects. Similarly 3%-13% of the carbon is tied up in CO and CO2 frozen in nonpolar ices toward field stars, and 0.2%-6% toward embedded objects. These numbers imply that most of the N is in N2, and a significant fraction of the available O is in O2 in the most quiescent regions of dense clouds. Ultraviolet photolysis of these ices produces a variety of photoproducts including CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. XCN is not produced in these experiments, placing important constraints on the origin of the enigmatic interstellar XCN feature. N2O and CO3 have not been previously considered as interstellar ice components.

NASA Discipline Exobiology↗

Effects of the 8 psia / 32% O2 Atmosphere on the Human in the Spaceflight Environment

Extravehicular activity (EVA) is at the core of a manned space exploration program. There are elements of exploration that may be safely and effectively performed by robots, but there are critical elements of exploration that will require the trained, assertive, and reasoning mind of a human crewmember. To effectively use these skills, NASA needs a safe, effective, and efficient EVA component integrated into the human exploration program. The EVA preparation time should be minimized and the suit pressure should be low to accommodate EVA tasks without undue fatigue, physical discomfort, or suit-related trauma. Commissioned in 2005, the Exploration Atmospheres Working Group (EAWG) had the primary goal of recommending to NASA an internal environment that allowed efficient and repetitive EVAs for missions that were to be enabled by the former Constellation Program. At the conclusion of the EAWG meeting, the 8.0 psia and 32% oxygen (O2) environment were recommended for EVA intensive phases of missions. As a result of selecting this internal environment, NASA gains the capability for efficient EVA with low risk of decompression sickness (DCS), but not without incurring additional negative stimulus of hypobaric hypoxia to the already physiologically challenging spaceflight environment. This paper provides a literature review of the human health and performance risks associated with the 8 psia/32% O2 environment. Of most concern are the potential effects on the central nervous system including increased intracranial pressure, visual impairment, sensorimotor dysfunction, and oxidative damage. Other areas of focus include validation of the DCS mitigation strategy, incidence and treatment of acute mountain sickness (AMS), development of new exercise countermeasures protocols, effective food preparation at 8 psia, assurance of quality sleep, and prevention of suit-induced injury. As a first effort, the trade space originally considered in the EAWG was re-evaluated looking for ways to decrease the hypoxic dose by further enriching the O2% or increasing the pressure. After discussion with the NASA engineering and materials community, it was determined that the O2 could be enriched from 32% to 34% and the pressure increased from 8.0 to 8.2 psia without significant penalty. These two small changes increase alveolar O2 pressure by 11 mmHg, which is expected to significantly benefit crewmembers. The 8.2/34 environment (inspired O2 pressure = 128 mmHg) is also physiologically equivalent to the staged decompression atmosphere of 10.2 psia / 26.5% O2 (inspired O2 pressure = 127 mmHg) used on 34 different shuttle missions for approximately a week each flight. Once decided, the proposed internal environment, if different than current experience, should be evaluated through appropriately simulated research studies. In many cases, the human physiologic concerns can be investigated effectively through integrated multi-discipline ground-based studies. Although missions proposing to use an 8.2/34 environment are still years away, it is recommended that these studies begin early enough to ensure that the correct decisions pertaining to vehicle design, mission operational concepts, and human health countermeasures are appropriately informed.

Environmental control↗

Convective and Diffusive O2 Transport Components of Peak Oxygen Uptake Following Long-duration Spaceflight

Spaceflight reduces aerobic capacity and may be linked with maladaptations in the O2 transport pathway. The aim was to 1) evaluate the cardiorespiratory adaptations following 6 months aboard the International Space Station and 2) model the contributions of convective (Q (raised dot) O2) and peripheral diffusive (DO2) components of O2 transport to changes in peak O2 uptake (V (raised dot) O2PEAK). To date, 1 male astronaut (XX yrs) completed an incremental exercise test to measure V (raised dot) O2PEAK prior to and 2 days post-flight. Cardiac output (Q (raised dot) ) was measured at three submaximal work rates via carbon dioxide rebreathing. The Q (raised dot) :V (raised dot) O2 relationship was extrapolated to V (raised dot) O2PEAK to determine Q (raised dot) PEAK. Hemoglobin concentration was measured at rest via a venous blood sample. These measurements were used to model the changes in Q (raised dot) O2 and DO2 using Fick's principle of mass conservation and Law of Diffusion as established by Wagner and colleagues (Annu. Rev. Physiol 58: 21-50, 1996 and J. Appl. Physiol. 73: 1067-1076, 1992). V (raised dot) O2PEAK decreased postflight from 3.72 to 3.45 l min-1, but Q (raised dot) PEAK increased from 24.5 to 27.7 l min-1. The decrease in V (raised dot) O2PEAK post-flight was associated with a 21.2% decrease in DO2, an 18.6% decrease in O2 extraction, but a 3.4% increase in Q (raised dot) O2. These preliminary data suggest that long-duration spaceflight reduces peripheral diffusing capacity and that it largely contributes to the post-flight decrease in aerobic capacity.

Ade, Carl J.↗

Extensive MRO CRISM Observations of 1.27 micron O2 Airglow in Mars Polar Night and Their Comparison to MRO MCS Temperature Profiles and LMD GCM Simulations

The Martian polar night distribution of 1.27 micron (0-0) band emission from O2 singlet delta [O2(1Delta(sub g))] is determined from an extensive set of Mars Reconnaissance Orbiter (MRO) Compact Reconnaissance Imaging Spectral Mapping (CRISM) limb scans observed over a wide range of Mars seasons, high latitudes, local times, and longitudes between 2009 and 2011. This polar nightglow reflects meridional transport and winter polar descent of atomic oxygen produced from CO2 photodissociation. A distinct peak in 1.27 micron nightglow appears prominently over 70-90NS latitudes at 40-60 km altitudes, as retrieved for over 100 vertical profiles of O2(1Delta(sub g)) 1.27 micron volume emission rates (VER). We also present the first detection of much (x80+/-20) weaker 1.58 micron (0-1) band emission from Mars O2(1Delta(sub g)). Co-located polar night CRISM O2(1Delta(sub g)) and Mars Climate Sounder (MCS) (McCleese et al., 2008) temperature profiles are compared to the same profiles as simulated by the Laboratoire de Météorologie Dynamique (LMD) general circulation/photochemical model (e.g., Lefèvre et al., 2004). Both standard and interactive aerosol LMD simulations (Madeleine et al., 2011a) underproduce CRISM O2(1Delta(sub g)) total emission rates by 40%, due to inadequate transport of atomic oxygen to the winter polar emission regions. Incorporation of interactive cloud radiative forcing on the global circulation leads to distinct but insufficient improvements in modeled polar O2(1Delta(sub g)) and temperatures. The observed and modeled anti-correlations between temperatures and 1.27 mm band VER reflect the temperature dependence of the rate coefficient for O2(1Delta(sub g)) formation, as provided in Roble (1995).

Atmosphere↗

Isotopic Ordering in Atmospheric O2 as a Tracer of Ozone Photochemistry and the Tropical Atmosphere

The distribution of isotopes within O2 molecules can be rapidly altered when they react with atomic oxygen. This mechanism is globally important: while other contributions to the global budget of O2 impart isotopic signatures, the O(3P) + O2 reaction resets all such signatures in the atmosphere on subdecadal timescales. Consequently, the isotopic distribution within O2 is determined by O3 photochemistry and the circulation patterns that control where that photochemistry occurs. The variability of isotopic ordering in O2 has not been established, however. We present new measurements of 18O18O in air (reported as delta36 values) from the surface to 33 km altitude. They confirm the basic features of the clumped-isotope budget of O2: Stratospheric air has higher delta36 values than tropospheric air (i.e., more 18O18O), reflecting colder temperatures and fast photochemical cycling of O3. Lower delta36 values in the troposphere arise from photochemistry at warmer temperatures balanced by the influx of high-delta36 air from the stratosphere. These observations agree with predictions derived from the GEOS-Chem chemical transport model, which provides additional insight. We find a link between tropical circulation patterns and regions where delta36 values are reset in the troposphere. The dynamics of these regions influences lapse rates, vertical and horizontal patterns of O2 reordering, and thus the isotopic distribution toward which O2 is driven in the troposphere. Temporal variations in delta36 values at the surface should therefore reflect changes in tropospheric temperatures, photochemistry, and circulation. Our results suggest that the tropospheric O3 burden has remained within a +/-10 percent range since 1978.

oxygen↗

The dayglow of the O2 atmospheric band system

The dayglow of the O2 atmospheric O2(1Sigma) band system has been simulated by taking into account the three main production mechanisms of the O2(1Sigma) state resonance fluorescence, a photochemical term due to quenching of O(1D), and a pure chemical process. Values of the emission rate, which are involved in the resonant scattering of the O2 atmospheric bands (A, B, and gamma), have been obtained as a function of altitude (0-120 km) and solar zenith angle using a line-by-line calculation. The values of the emission rate, along with updated rate coefficients, have been used in the calculation of the production rate of O2(1Sigma) and the volume emission rate of the (O2 1Sigma, v prime = 0)-(O2 3Sigma, v double prime = 0) transition. The results of these calculations are compared to observational measurements and are found to be in excellent agreement.

Bucholtz, A.↗

The effect of the isotopic composition of oxygen on the non-mass-dependent isotopic fractionation in the formation of ozone by discharge of O2

Isotopic fractionation processes in the formation of O3 by 20-kV 60-kHz discharge of O2 in a fused silica container at 77 K are investigated experimentally, with a focus on the effects of changes in the isotopic composition of O2, the O2 pressure, the degree of O3 formation, and the discharge geometry on the isotope abundances in the postdischarge O2 and O3. The results are presented in tables and graphs and compared with the predictions of theoretical models involving vibrational anharmonicity and symmetry effects on O3 predissociation. In experiments using O2 enriched with O-17 and O-18, the heavy isotope is enriched in the residual O2 and not in the O3, whereas the opposite is true when atmospheric isotope abundances are used. It is inferred that the predissociation rate depends on the symmetry and mass of the O3 molecules and not on self-shielding or symmetry effects in the reactant O2. The potential value of the present findings for studies of anomalous isotope abundances in meteorites is indicated.

Yang, Jongmann↗

Oscillatory shear stress stimulates endothelial production of O2- from p47phox-dependent NAD(P)H oxidases, leading to monocyte adhesion

Arterial regions exposed to oscillatory shear (OS) in branched arteries are lesion-prone sites of atherosclerosis, whereas those of laminar shear (LS) are relatively well protected. Here, we examined the hypothesis that OS and LS differentially regulate production of O2- from the endothelial NAD(P)H oxidase, which, in turn, is responsible for their opposite effects on a critical atherogenic event, monocyte adhesion. We used aortic endothelial cells obtained from C57BL/6 (MAE-C57) and p47phox-/- (MAE-p47-/-) mice, which lack a component of NAD(P)H oxidase. O2- production was determined by dihydroethidium staining and an electron spin resonance using an electron spin trap methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine. Chronic exposure (18 h) to an arterial level of OS (+/- 5 dynes/cm2) increased O2- (2-fold) and monocyte adhesion (3-fold) in MAE-C57 cells, whereas chronic LS (15 dynes/cm2, 18 h) significantly decreased both monocyte adhesion and O2- compared with static conditions. In contrast, neither LS nor OS were able to induce O2- production and monocyte adhesion to MAE-p47-/-. Treating MAE-C57 with a cell-permeable superoxide dismutase compound, polyethylene glycol-superoxide dismutase, also inhibited OS-induced monocyte adhesion. In addition, over-expressing p47phox in MAE-p47-/- restored OS-induced O2- production and monocyte adhesion. These results suggest that chronic exposure of endothelial cells to OS stimulates O2- and/or its derivatives produced from p47phox-dependent NAD(P)H oxidase, which, in turn, leads to monocyte adhesion, an early and critical atherogenic event.

NASA Program Fundamental Space Biology↗

Room-temperature Broadening and Pressure-shift Coefficients in the nu(exp 2) Band of CH3D-O2: Measurements and Semi-classical Calculations

We report measured Lorentz O2-broadening and O2-induced pressure-shift coefficients of CH3D in the nu(exp 2) fundamental band. Using a multispectrum fitting technique we have analyzed 11 laboratory absorption spectra recorded at 0.011 cm(exp 1) resolution using the McMath-Pierce Fourier transform spectrometer, Kitt Peak, Arizona. Two absorption cells with path lengths of 10.2 and 25 cm were used to record the spectra. The total sample pressures ranged from 0.98 to 339.85 Torr with CH3D volume mixing ratios of 0.012 in oxygen. We report measurements for O2 pressure-broadening coefficients of 320 nu(exp 2) transitions with quantum numbers as high as J0(sup w) = 17 and K = 14, where K(sup w) = K' is equivalent to K (for a parallel band). The measured O2-broadening coefficients range from 0.0153 to 0.0645 cm(exp -1) atm(exp -1) at 296 K. All the measured pressure-shifts are negative. The reported O2-induced pressure-shift coefficients vary from about -0.0017 to -0.0068 cm(exp -1) atm(exp -1). We have examined the dependence of the measured broadening and shift parameters on the J(sup W), and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = -J(sup W), J(sup W), and J(sup w) + 1 in the QP-, QQ-, and QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.4%. The O2-broadening and pressure shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are generally larger than the experimental data. Using for the trajectory model an isotropic Lennard-Jones potential derived from molecular parameters instead of the spherical average of the atom-atom model, a better agreement is obtained with these data, especially for |m| <= 12 values (11.3% for the first calculation and 8.1% for the second calculation). The O2-pressure shifts whose vibrational contribution are either derived from parameters fitted in the QQ-branch of selfinduced shifts of CH3D or those obtained from pressure shifts induced by Xe in the nu(sup 3) band of CH3D are in reasonable agreement with the scattered experimental data (17.0% for the first calculation and 18.7% for the second calculation).

Predoi-Cross, Adriana↗

Reaction of NH2 with NO and O2

Experiments were performed on the photooxidation of NH3 at room temperature and the photolysis of NH3-NO mixtures in order to determine the reaction paths of NH2 with O2. NH3 was photolyzed (NH3 + E yields NH2 + H) in the presence of O2 above 0.6 torr at 213.9 nm and 25 C, producing N2 and N2O. Only N2 and N2O were produced with any significant quantum yield, and their quantum yield was invariant with reaction conditions, which imposes a great number of constraints reducing the number of possible reactions greatly. It is argued that the N2 must be produced from the NH2O2 radical which was produced by the reaction between NH2 and O2. Subsequent reactions leading to N2 and N2O are speculative. In the photolysis of NH3 in the presence of NO and NO-O2 mixtures, the products identified were N2, H2, and N2O. Without the presence of O2, the reaction scheme after photolysis is (2) NH2 + NO yields N2 + H2O, (3) H + NO + M yields HNO + M, (4) H + HNO yields H2 + NO, and (5) 2HNO yields N2O + H2O. The average value for the ratio k3 times the square root of k5 divided by k4 was computed to be (1.6 plus or minus 0.6) times 10 to the minus 28th cm to the exponent 9/2 per square root sec. In addition, the presence of 113 mtorr of O2 had no effect on the quantum yields of N2 or H2, so it appears that it does not deactivate electronically excited NH3.

Jayanty, R. K. M.↗

A laboratory study on the dissociative recombination of vibrationally excited O2/+/ions

The dissociative recombination of vibrationally excited O2(+) ions is studied in light of the possible importance of this reaction in upper atmospheric chemistry. A plasma spectroscopy experiment was performed in a microwave cavity filled by an argon-oxygen mixture, with O(1S) production monitored by measurements of the 5577-A afterglow, the O2(+) density and the electron concentration. Plasma and optical data reveal the predominant afterglow ions to be Ar2(+) and O2(+), with an effective O(1S) dissociative recombination coefficient of 2.1 x 10 to the -8th cu cm/sec, corresponding to a quantum yield of 10%. Experiments with an argon-krypton-oxygen mixture reveal that vibrationally excited O2(+) ions are the chief source of the O(1S) atoms, with a specific recombination coefficient for the dissociation of O2(+)(2 pi g) into O(1S) and O(1D) of 4.2 x 10 to the -9th cu cm/sec. A comparison of the laboratory results with Atmospheric Explorer data on the 5577-A airglow implies that O2(+) ions in the sunlit ionosphere are vibrationally excited to the same degree as in the laboratory, with the vibrational relaxation of these ions much slower than dissociative recombination. Results also predict a dawn-twilight asymmetry in the effective O(1S) yield due to the normal variation of electron content.

Zipf, E. C.↗

Device for quickly sensing the amount of O2 in a combustion product gas

A sensing device comprising an O2 sensor, a pump, a compressor, and a heater is provided to quickly sense the amount of O2 in a combustion product gas. A sample of the combustion product gas is compressed to a pressure slightly above one atmosphere by the compressor. Next, the heater heats the sample between 800 C and 900 C. Next, the pump causes the sample to be flushed against the electrode located in O2 sensor 6000 to 10,000 times per second. Reference air at approximately one atmosphere is provided to the electrode of O2 sensor. Accordingly, the O2 sensor produces a voltage which is proportional to the amount of oxygen in the combustion product gas. This voltage may be used to control the amount of O2 entering into the combustion chamber which produces the combustion product gas.

Singh, Jag J.↗

SME observations of O2(1 Delta g) nightglow - An assessment of the chemical production mechanisms

Solar Mesosphere Explorer (SME) observations of the 3 a.m. 1.27 micron nightglow at 45 N latitude are reported. From the deduced volume emission rates, the O2(a 1 Delta g) nighttime production rates for the 80-100 km altitude range are derived. Utilizing the mean SME-acquired 3 p.m. ozone profile for the same latitude and time period and an updated photochemical model, nighttime O, O3, H, OH, HO2, and H2O2 profiles are determined. These are used in calculating the rates of reactions which are sufficiently exothermic to produce O2(1 Delta) or excited states of OH or HO2, which could transfer their energy to O2 to form O2(1 Delta). Yields of O2(1 Delta) based on published laboratory and observational studies are used to find that the sum of two reaction sequences can approximate the SME measurements: (1) O + O + M and (2) H + O3 followed by OH-asterisk + O2.

Howell, Colin D.↗