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Hypersonic inviscid flow past a circular cylinder with nonequilibrium oxygen dissociation and dissociation of the free stream
Two different interpretations of measured dissociation rate constants and effects on coupled vibrational dissociational flows of oxygen over wedge
Hypersonic flow of air past circular cylinder with nonequilibrium oxygen dissociation, including dissociation of free stream
Hypersonic flow of air past circular cylinder with nonequilibrium oxygen dissociation, including dissociation of free stream
A nitrous oxide-based oxygen-supply system (NOBOSS) is an apparatus in which a breathable mixture comprising 2/3 volume parts of N2 and 1/3 volume part of O2 is generated through dissociation of N2O. The NOBOSS concept can be adapted to a variety of applications in which there are requirements for relatively compact, lightweight systems to supply breathable air. These could include air-supply systems for firefighters, divers, astronauts, and workers who must be protected against biological and chemical hazards. A NOBOSS stands in contrast to compressed-gas and cryogenic air-supply systems. Compressed-gas systems necessarily include massive tanks that can hold only relatively small amounts of gases. Alternatively, gases can be stored compactly in greater quantities and at low pressures when they are liquefied, but then cryogenic equipment is needed to maintain them in liquid form. Overcoming the disadvantages of both compressed-gas and cryogenic systems, the NOBOSS exploits the fact that N2O can be stored in liquid form at room temperature and moderate pressure. The mass of N2O that can be stored in a tank of a given mass is about 20 times the mass of compressed air that can be stored in a tank of equal mass. In a NOBOSS, N2O is exothermically dissociated to N2 and O2 in a main catalytic reactor. In order to ensure the dissociation of N2O to the maximum possible extent, the temperature of the reactor must be kept above 400 C. At the same time, to minimize concentrations of nitrogen oxides (which are toxic), it is necessary to keep the reactor temperature at or below 540 C. To keep the temperature within the required range throughout the reactor and, in particular, to prevent the formation of hot spots that would be generated by local concentrations of the exothermic dissociation reaction, the N2O is introduced into the reactor through an injector tube that features carefully spaced holes to distribute the input flow of N2O widely throughout the reactor. A NOBOSS includes one or more "destroyer" subsystems for removing any nitrogen oxides that remain downstream of the main N2O-dissociation reactor. A destroyer includes a carbon bed in series with a catalytic reactor, and is in thermal contact with the main N2O-dissociation reactor. The gas mixture that leaves the main reactor first goes through a carbon bed, which adsorbs all of the trace NO and most of the trace NO2. The gas mixture then goes through the destroyer catalytic reactor, wherein most or all of the remaining NO2 is dissociated. A NOBOSS can be designed to regulate its reactor temperature across a range of flow rates. One such system includes three destroyer loops; these loops act, in combination with a heat sink, to remove heat from the main N2O-dissociation reactor. In this system, the N2O and product gases play an additional role as coolants; thus, as needed, the coolant flow increases in proportion to the rate of generation of heat, helping to keep the main-reactor temperature below 540 C.
A theoretical study of vibrational excitations and dissociations of nitrogen undergoing a nonequilibrium relaxation process upon heating and cooling is reported. The rate coefficients for collisional induced vibrational transitions and transitions from a bound vibrational state into a dissociative state have been calculated using an extension of the theory originally proposed by Schwarz (SSH) et al. (1952). High-lying vibrational states and dissociative states were explicitly included but rotational energy transfer was neglected. The transition probabilities calculated from the SSH theory were fed into the master equation, which was integrated numerically to determine the population distribution of the vibrational states as well as bulk thermodynamic properties. The results show that: (1) the transition rates have a minimum near the middle of the bound vibrational levels, causing a bottleneck in the vibrational relaxation and dissociation rates; (2) high vibrational states are always in equilibrium with the dissociative state; (3) for the heating case, only the low vibrational states relax according to the Landau-Teller theory; (4) for the cooling case, vibrational relaxation cannot be described by a rate equation; (5) Park's (1985, 1988) two-temperature model is approximately valid; and (6) the average vibrational energy removed in dissociation is about 30 percent of the dissociation energy.
We report a theoretical study of the dissociative ionization (DI) and product distributions of benzene (C6H6) and pyridine (C5H5N) from their low-lying ionization channels. Our approach makes use of the fact that electronic motion is much faster than nuclear motion allowing DI to be treated as a two-step process. The first step is the electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step, the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model [W.M. Huo, Phys. Rev. A64,042719-I (2001)]. For the unimolecular dissociation, we use multiconfigurational self-consistent field (MCSCF) methods to determine the steepest descent pathways to the possible product channels. More accurate methods are then used to obtain better energetics of the paths which are used to determine unimolecular dissociation probabilities and product distributions. Our analysis of the dissociation products and the thresholds of their productions for benzene are compared with the recent dissociative photoionization meausurements of benzene by Feng et al. [R. Feng, G. Cooper, C.E. Brion, J. Electron Spectrosc. Relat. Phenom. 123,211 (2002)] and the dissociative photoionization measurements of pyridine by Tixier et al. [S. Tixier, G. Cooper, R. Feng, C.E. Brion, J. Electron Spectrosc. Relat. Phenom. 123,185 (2002)] using dipole (e,e+ion) coincidence spectroscopy.
Free secondary electrons are the most abundant secondary species in ionizing radiation. Their role in DNA damage, both direct and indirect, is an active area of research. While indirect damage by free radicals, particularly by the hydroxyl radical generated by electron collision with water. is relatively well studied, damage by direct electron collision with DNA is less well understood. Only recently Boudaiffa et al. demonstrated that electrons at energies well below ionization thresholds can induce substantial yields of single- and double-strand breaks in DNA by a resonant, dissociative attachment process. This study attracted renewed interest in electron collisions with DNA, especially in the low energy region. At higher energies ionization becomes important. While Monte Carlo track simulations of radiation damage always include ionization, the probability of dissociative ionization, i.e., simultaneous ionization and dissociation, is ignored. Just like dissociative attachment, dissociative ionization may be an important contributor to double-strand breaks since the radicals and ions produced by dissociative ionization, located in the vicinity of the DNA coil, can readily interact with other parts of the DNA. Using the improved binary-encounter dipole (iBED) formulation, we calculated the ionization cross sections of the four DNA bases, adenine, cytosine, guanine, and thymine, by electrons at energies from threshold to 1 KeV. The present calculation gives cross sections approximately 20% lower than the results by Bemhardt and Paretzke using the Deutsch-Mark and Binary-Encounter-Bethe (BEB) formalisms. The difference is most likely due to the lack of a shielding term in the dipole potential used in the Deutsch-Mark and BEB formalisms. The dissociation channels of ionization for the bases are currently being studied.
Dissociated and steam reformed methanol were evaluated as automotive engine fuels. Advantages and disadvantages in using methanol in the reformed rather than liquid state were discussed. Engine dynamometer tests were conducted with a four cylinder, 2.3 liter, spark ignition automotive engine to determine performance and emission characteristics operating on simulated dissociated and steam reformed methanol (2H2 + CO and 3H2 + CO2 respectively), and liquid methanol. Results are presented for engine performance and emissions as functions of equivalence ratio, at various throttle settings and engine speeds. Operation on dissociated and steam reformed methanol was characterized by flashback (violent propagation of a flame into the intake manifold) which limited operation to lower power output than was obtainable using liquid methanol. It was concluded that: an automobile could not be operated solely on dissociated or steam reformed methanol over the entire required power range - a supplementary fuel system or power source would be necessary to attain higher powers; the use of reformed mechanol, compared to liquid methanol, may result in a small improvement in thermal efficiency in the low power range; dissociated methanol is a better fuel than steam reformed methanol for use in a spark ignition engine; and use of dissociated or steam reformed methanol may result in lower exhaust emissions compared to liquid methanol.
Observations of the H Lyman(alpha) (Ly-alpha) emission from Jupiter have shown pronounced emissions, exceeding solar fluorescence, in the polar aurora and equatorial "bulge" regions. The H Ly-alpha line profiles from these regions are broader than expected, indicating high-energy processes producing fast atoms as determined from the observed Doppler broadening. Toward understanding that process a high-resolution ultraviolet (UV) spectrometer was employed for the first measurement of the H Ly-alpha emission Doppler profile from dissociative excitation of H2 by electron impact. Analysis of the deconvolved line profile reveals the existence of a narrow central peak of 40 +/- 4 mA full width at half maximum and a broad pedestal base about 240 mA wide. Two distinct dissociation mechanisms account for this Doppler structure. Slow H(2p) atoms characterized by a distribution function with peak energy near 80 meV produce the peak profile, which is nearly independent of the electron impact energy. Slow H(2p) atoms arise from direct dissociation and predissociation of singly excited states which have a dissociation limit of 14.68 eV. The wings of H Ly-alpha arise from dissociative excitation of a series of doubly excited states which cross the Franck-Condon region between 23 and 40 eV. The profile of the wings is dependent on the electron impact energy, and the distribution function of fast H(2p) atoms is therefore dependent on the electron impact energy. The fast atom kinetic energy distribution at 100 eV electron impact energy spans the energy range from 1 to 10 eV with a peak near 4 eV. For impact energies above 23 eV the fast atoms contribute to a slightly asymmetric structure of the line profile. The absolute cross sections of the H Ly-alpha line peak and wings were measured over the range from 0 to 200 eV. Analytic model coefficients are given for the measured cross sections which can be applied to planetary atmosphere auroral and dayglow calculations. The dissociative excitation process, while one contributing process, appears insufficient by itself to explain the line broadening observed at Jupiter.
We report a theoretical study of the dissociative ionization (DI) of benzene from the low-lying ionization channels. Our approach makes use of the fact that electron motion is much faster than nuclear motion and DI is treated as a two-step process. The first step is electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model. For the unimolecular dissociation step, we study the steepest descent reaction path to the minimum of the ion potential energy surface. The path is used to analyze the probability of unimolecular dissociation and to determine the product distributions. Our analysis of the dissociation products and the thresholds of the productions are compared with the result dissociative photoionization measurements of Feng et al. The partial oscillator strengths from Feng et al. are then used in the iBED cross section calculations.
Time-of-flight techniques have been used to investigate the electron-impact dissociation of H2, HD, and D2 in order to determine the effect of isotopic mass variation in the target molecule on the dissociative excitation process. At incident electron energies near 100 eV, the time-of-flight spectrum produced from each molecule consists of atoms in the metastable 2s state and in high-lying long-lived Rydberg levels. The individual time-of-flight distributions, kinetic-energy spectra, and relative differential cross sections for these two species resulting from each molecule have been measured. The kinetic-energy spectrum of the Rydberg atoms produced from dissociative excitation of H2 was notably dissimilar in shape from the corresponding distributions produced from HD and D2. Also the 2s and Rydberg production cross sections differed between the three molecules. In the dissociation of the heteronuclear HD molecule, the ratio of fast H(2s) atoms to D(2s) atoms was about 1 to 1, while the same ratio comparing the Rydberg atoms was nearly 2 to 1. These differences indicate the influence of the mass variation on the position of the Franck-Condon region in the production of 2s atoms and on the competition between autoionization and dissociation in the formation of Rydberg fragments.
The collisionless dissociation of SF6 has been studied using simultaneous irradiation by two frequencies from a CO2 laser which are both nearly resonant with the SF6nu3 absorption band. It was found that the dissociation was enhanced, and occurred over a wider frequency range, than for single frequency dissociation. No threshold effect was observed for a weak resonant and a much higher energy field pumping slightly off-resonance. For such two frequency irradiation, the peak in the dissociation curve was found to be shifted to lower frequencies with respect to that for single frequency dissociation.
The spectral line shapes of the radiation emitted from O atoms produced by the dissociative excitation of O2, CO, CO2 and NO are investigated. Doppler line shapes are derived from time-of-flight spectra of O (5S0) atoms decaying by the emission of 1356-A radiation after being produced in electron impact experiments at incident electron energies from 25 to 300 eV. It is shown that the effective line width of the radiation is large compared with the Doppler absorption widths of ambient O atoms in both photoelectron and auroral excitation, and thus the dissociatively excited component of the O I 1304-A airglow will behave as though it were optically thin, exhibiting pronounced limb brightening effects and a scale height characteristic of the initial, local source function. It is found that the average kinetic energy of the dissociation fragments inferred from O I (5S) time-of-flight spectra is in good agreement with that of O I (3S) atoms in the electron impact dissociation of CO2, although not for O2. Finally, it is suggested that although electron impact dissociation of CO and CO2 contributes to the 1304-A emission in the upper atmosphere of Venus, it cannot be the dominant source of this radiation since the absolute cross sections for the reaction are too small.
The Landau-Zener theory of reactive cross sections has been applied to diatomic molecules dissociating from a ladder of rotational and vibrational states. Although the preexponential factor of the Arrhenius rate expression is shown to be a complex function of the dimensionless activation energy, the average over all states in the ladder is well represented by a single factor that varies about as T exp (-n), where the coefficient n is the order of unity. This relation agrees very well with experimental data for dissociation of O2 and N2, for example. The results validate previous empirical assignment of a single preexponential factor in the Arrhenius expression and justify the extrapolation of the expression well beyond the range of data. The theory is then used to calculate the effect of vibrational nonequilibrium on dissociation rate. For Morse oscillators the results are about the same as for harmonic oscillators, and the dissociation from a ladder of equilibrium rotational and nonequilibrium vibrational states is close to an analytic approximation provided by Hammerling, Kivel, and Teare for harmonic oscillators all dissociating from the ground rotational state.
The goal of this work is the identification of states especially as related to the process of error production and lapses of awareness as might be experienced during aviation. Given the need for further articulation of the characteristics of 'error prone state' or 'hazardous state of awareness,' this NASA grant focused on basic ground work for the study of the psychophysiology of these states. In specific, the purpose of this grant was to establish the necessary methodology for addressing three broad questions. The first is how the error prone state should be conceptualized, and whether it is similar to a dissociative state, a hypnotic state, or absent mindedness. Over 1200 subjects completed a variety of psychometric measures reflecting internal states and proneness to mental lapses and absent mindedness; the study suggests that there exists a consistency of patterns displayed by individuals who self-report dissociative experiences such that those individuals who score high on measures of dissociation also score high on measures of absent mindedness, errors, and absorption, but not on scales of hypnotizability. The second broad question is whether some individuals are more prone to enter these states than others. A study of 14 young adults who scored either high or low on the dissociation experiences scale performed a series of six tasks. This study suggests that high and low dissociative individuals arrive at the experiment in similar electrocortical states and perform cognitive tasks (e.g., mental math) in a similar manner; it is in the processing of internal emotional states that differences begin to emerge. The third question to be answered is whether recent research in nonlinear dynamics, i.e., chaos, offer an addition and/or alternative to traditional signal processing methods, i.e., fast Fourier transforms, and whether chaos procedures can be modified to offer additional information useful in identifying brain states. A preliminary review suggests that current nonlinear dynamical techniques such as dimensional analysis can be successfully applied to electrocortical activity. Using the data set developed in the study of the young adults, chaos analyses using the Farmer algorithm were performed; it is concluded that dimensionality measures reflect information not contained in traditional EEG Fourier analysis.
SRI International undertook a novel experimental measurement of the product states formed by dissociative recombination (DR) of O2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and rovibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates. For a molecular ion such as O2(+), the dissociation recombination reaction is (1) O2(+) + e yields O + O + W. The atomic products of this reaction, in this case two oxygen atoms, can be produced in a variety of excited states and with a variety of kinetic energies, as represented by W in Eq. (1). These atoms are not only active in the neutral chemistry of the ionosphere, but are also especially important because their optical emissions are often used to infer in situ concentrations of the parent molecular ion and ambient electron densities. Many laboratory measurements have been made of DR reaction rates under a wide range of electron temperatures, but very little is known about the actual distributions among the final states of the atomic products. This lack of knowledge seriously limits the validity and effectiveness of efforts to model both natural and man-made ionospheric disturbances. Bates recently identified major deficiencies in the currently accepted branching ratios for O2(+) as they relate to blue and green line emission measurements in the nocturnal F-region. During our two-year effort, we partially satisfied our ambitious goals. We constructed and operated a variable pressure, electron-impact ion source and a high pressure, hollow-cathode discharge ion source for O2(+), NO(+), and N2(+) beams. Translational spectroscopy of the products of dissociative charge transfer in Cs vapor was used to accurately assay the composition of the O2(+) and NO(+) beams and to develop a methodology for the vibrationally controlled preparation of the ground state ion beams. Attempts to assay the N2(+) beam revealed a novel two-electron process in the charge transfer reactions. A coaxial electron gun for the DR measurements was constructed following an extensive numerical design of the fields. Tests of the gun, however, found substantial perturbations of the magnetic fields by the soft iron (CMI-C) assembly containing the Langmuir probe that locates the electron beam. Hydrogen annealing of the iron failed to eliminate the field perturbations, necessitating the removal of the probe assembly. During this work on the coaxial electron gun, we discovered that predissociated high Rydberg states of O2 could be produced by subjecting the molecules to a sudden perturbation by an electromagnetic field. This technique allowed a measurement of the product branching to the atomic limits for the lowest seven vibrational levels of O2(+).
The Doppler profiles of one of the fine structure lines of the N I (1200 A) g (sup 4)S(sup 0)-(sup 4)P multiplet and of the N II (1085 A) g (sup 3)p(sup O)-(sup 3)D multiplet have been measured. Excitation of the multiplets is produced by electron impact dissociative excitation of N2. The experimental line profiles are evaluated by fast Fourier transform (FFT) techniques and analysis of the profiles yields the kinetic energy distribution of fragments. The full width at half maximum (FWHM) of N I (1200 A) increases from 27+/-6 mA at 30 eV to 37+/-4 mA at 100 eV as the emission cross section of the dissociative ionization excitation process becomes more important relative to the dissociative excitation process. The FWHM of the N II (1085 A) line is 36+/-4 mA at 100 eV. For each multiplet the kinetic energy distribution function of each of the two fragment N atoms (ions) is much broader than thermal with a mean energy above 1.0 eV. The dissociation process with the largest cross section is predissociation and predominantly produces N atoms with kinetic energy distributions having mean energies above 0.5 eV. Dissociative processes can lead to a substantial escape flux of N I atoms from the satellites, Titan and Triton of the outer planets.