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Absorption cross sections of electronic band systems of diatomic nitrogen, oxygen, carbon, nitrogen oxide, and carbon-nitrogen molecules at high temperatures
The problem is analyzed for the case of hydrogen fuel, taking into account supersonic and hypersonic vehicles using scramjet engines. The combustion in scramjets occurs at very high velocity and in a short time. In scramjet combustor designs, two different criteria can be used to design the engine. The amount of NO formed in the diffusion flame depends substantially on the maximum temperature reached. Effects of changing the mode of combustion from a diffusion flame to a heat conduction flame are considered, giving attention to the amount of NO produced in an engine of a given design.
The objectives of the reported investigation included the demonstration of a system in which combustion can be maintained under very lean conditions. Aspects of pollutant formation and the stability characteristics of the system were studied. An opposed reacting jet model laboratory combustor was employed in the experiments. Results obtained with the aid of an analytical modeling technique based on the computational scheme reported by Gosman et al. (1969) are also presented. The investigation indicates that fuel lean combustion might provide an effective means of achieving low pollutant emission levels.
The NOx pollution problem of hydrogen fueled turbojets and supersonic combustion ramjets (scramjets) was investigated to determine means of substantially alleviating the problem. Since the NOx reaction rates are much slower than the energy producing reactions, the NOx production depends mainly on the maximum local temperatures in the combustor and the NOx concentration is far from equilibrium at the end of a typical combustor (L approximately 1 ft). In diffusion flames, as used in present turbojets and scramjets combustor designs, the maximum local temperature occurs at the flame and is equal to the stoichiometric value. Whereas, in the heat conduction flames, wherein the flame propagates due to a heat conduction process away from the flame to the cooler oncoming premixed unburnt gases, the maximum temperature is lower than in the diffusion flame. Hence the corresponding pollution index is also lower.
Experimental results of exit plane NO/NO(x) emissions from atmospheric monodisperse fuel spray combustion are presented. Six different hydrocarbon fuels were studied: isopropanol, n-propanol, n-octane, iso-octane, n-heptane and methanol. The results indicate an optimum droplet size for minimizing NO/NO(x) production for all of the test fuels. At the optimum droplet diameter, reductions in NO/NO(x) relative to the NO(x) occurred at droplet diameters of 55 and 48 microns respectively, as compared to a 50-micron droplet size for isopropanol. The occurrence of the minimum NO(x) point at different droplet diameters for the different fuels appears to be governed by the extent of prevaporization of the fuel in the spray, and is consistent with theoretical calculations based on each fuel's physical properties. Estimates are also given for the behavior of heavy fuels and of polydisperse fuel sprays in shifting the minimum NO(x) point compared to a monodisperse situation.
While it is generally thought that the bactericidal effects of NO and NO2 derive from their reaction with water to form nitrous and nitric acids (Shank et al., 1962), this appears to be true only at high concentrations. The data presented here suggest that at low NO and NO2 concentrations, acids are not present in high enough concentrations to act as toxic agents. Reference is made to a study by Grant et al. (1979), which found that exposing acid forest soil to 1 ppm of NO2 did not cause the soil pH to drop. The results presented here show that at low concentrations of NO and NO2, the NO is bacteriostatic for some organisms and not for others, whereas NO2 may protect some bacteria from the inhibitory effects of NO. Since it has been shown that bacteria can divide while airborne (Dimmick et al., 1979), the present results suggest that NO at the low concentrations found in the atmosphere can select for resistant bacteria in the air and affect the viable airborne bacterial population.
A study of NO sub x formation in a one dimensional monodisperse spray combustion system, which allowed independent droplet size variation, was conducted. Temperature, NO and NO sub x concentrations were measured in the transition region, encompassing a 26 to 74 micron droplet size range. Emission measurements of hydrocarbons, carbon monoxide, carbon dioxide and oxygen were also made. The equivalence ratio was varied between 0.8 and 1.2 for the fuels used, including methanol, isopropanaol, n-heptane and n-octane. Pyridine and pyrrole were added to n-heptane as nitrogen-containing additives in order to simulate synthetic fuels. Results obtained from the postflame regions using the pure fuels indicate an optimum droplet size in the range of 43 to 58 microns for minimizing NO sub x production. For the fuels examined, the maximum NO sub x reductions relative to the small droplet size limit were about 10 to 20% for lean and 20 to 30% for stoichiometric and rich mixtures. This behavior is attributed to droplet interactions and the transition from diffusive to premixed type of burning. Preflame vaporization controls the gas phase stoichiometry which has a significant effect on the volume of the hot gases surrounding a fuel droplet, where NO sub x is formed.
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Glyoxal (CHOCHO) is produced in the atmosphere by the oxidation of volatile organic compounds(VOCs). Like formaldehyde (HCHO), another VOC oxidation product, it is measurable from space by solar backscatter. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the Southeast Nexus (SENEX) campaign over the southeast US in summer 2013 to better understand the CHOCHO time-dependent yield from isoprene oxidation, its dependence on nitrogen oxides (NO (sub x) triple bonded to NO plus NO2), the behavior of the CHOCHO-HCHO relationship, the quality of Ozone Monitoring Instrument (OMI) CHOCHO satellite observations, and the implications for using CHOCHO observations from space as constraints on isoprene emissions. We simulate the SENEX and OMI observations with the Goddard Earth Observing System chemical transport model (GEOSChem) featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NO (sub x) conditions following the isomerization of the isoprene peroxy radical (ISOPO2).The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NO (sub x) conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free-tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free-tropospheric background and show southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the southeast US are tightly correlated and provide redundant proxies of isoprene emissions. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NO (sub x) conditions apparent in the SENEX data.
Climate change can affect atmospheric composition through perturbation of natural processes, leading to complex feedbacks. The primary atmospheric oxidants OH and ozone are very sensitive to emissions of nitrogen oxides (NO x ) from lightning, and therefore so are the subsequent chemical perturbations to long-lived greenhouse gases (e.g., methane) and aerosol chemistry and physics. Meanwhile, cloud electrification responds to both meteorology and composition (aerosol particles). Key to understanding the ultimate impact of lightning on air quality and climate is the long-term methane feedback. Here, we present simulations from the GISS ModelE2.1 chemistry-climate model in which we isolate the response of Earth’s radiative budget and composition to lightning NO x in the present day and at the end of this century by allowing the model to re-equilibrate following removal of the source. Whereas lightning initially contributes to surface ozone enhancements, longer-term responses amplified by the methane lifetime feedback reduce surface ozone on multi-decadal time scales in the northern midlatitudes. Lightning consequently contributes a strong negative radiative effect in the present day (-0.5 W m -2 ), stronger than that estimated for the anthropogenic NOx source. In addition to influencing tropospheric composition, we find significant changes in stratospheric dynamics and composition. We test the sensitivity of our results to multiple parameterizations for global lightning activity.
High resolution absorption spectrograms of excited nitrogen oxide molecular interactions
Emissions of total oxides of nitrogen, nitric oxide, unburned hydrocarbons, carbon monoxide, and carbon dioxide from two J-58 afterburning turbojet engines at simulated high-altitude flight conditions are reported. Test conditions included flight speeds from Mach 2 to 3 at altitudes from 16.0 to 23.5 km. For each flight condition exhaust measurements were made for four or five power levels, from maximum power without afterburning through maximum afterburning. The data show that exhaust emissions vary with flight speed, altitude, power level, and radial position across the exhaust. Oxides of nitrogen emissions decreased with increasing altitude and increased with increasing flight speed. Oxides of nitrogen emission indices with afterburning were less than half the value without afterburning. Carbon monoxide and hydrocarbon emissions increased with increasing altitude and decreased with increasing flight speed. Emissions of these species were substantially higher with afterburning than without.
The ability to measure emissions from aeronautic engines and in commercial applications such as automotive emission control and chemical process monitoring is a necessary first step if one is going to actively control those emissions. One single sensor will not give all the information necessary to determine the chemical composition of a high-temperature, harsh environment. Rather, an array of gas sensor arrays--in effect, a high-temperature electronic "nose"--is necessary to characterize the chemical constituents of a diverse, high-temperature environment, such as an emissions stream. The signals produced by this nose could be analyzed to determine the constituents of the emission stream. Although commercial electronic noses for near-room temperature applications exist, they often depend significantly on lower temperature materials or only one sensor type. A separate development effort necessary for a high-temperature electronic nose is being undertaken by the NASA Glenn Research Center, Case Western Reserve University, Ohio State University, and Makel Engineering, Inc. The sensors are specially designed for hightemperature environments. A first-generation high-temperature electronic nose has been demonstrated on a modified automotive engine. This nose sensor array was composed of sensors designed for hightemperature environments fabricated using microelectromechanical-systems- (MEMS-) based technology. The array included a tin-oxide-based sensor doped for nitrogen oxide (NOx) sensitivity, a SiC-based hydrocarbon (CxHy) sensor, and an oxygen sensor (O2). These sensors operate on different principles--resistor, diode, and electrochemical cell, respectively--and each sensor has very different responses to the individual gases in the environment. A picture showing the sensor head for the array is shown in the photograph on the left and the sensors installed in the engine are shown in the photograph on the right. Electronics are interfaced with the sensors for temperature control and signal conditioning, and packaging designed for high temperatures is necessary for the array to survive the engine environment.
Rate of nitrogen oxide ion recombination in aurora
As part of our work on nitrogen-rich ices, the IR spectra and band strengths used in a recent paper to identify and quantify radiation-induced changes in an N2+H2O ice near 15 K are examined, along with reports of (i) a chemical tracer for N2+H2O ices, (ii) a new IR feature of solid N2, and (iii) a striking 15N isotopic enrichment. Problems are found for each IR band strength used and for each of the three claims made, to the extent that none are supported by the results presented to date. In contrast, new work presented here, combined with several older investigations, strongly supports the formation of di- and triatomic nitrogen oxides in irradiated N2-rich ices. Observations and trends in the chemistry of N2-rich icy solids are described, and conclusions are drawn. A considerable amount of material from previous chemical studies of N2-rich systems, spanning more than a century, is brought together for the rst time and used to examine the chemistry of N2-rich ices in extraterrestrial environments. Needs are identied and suggestions made for future studies of N2-rich interstellar and planetary ice analogs.