Unimolecular gas-phase hydrogen randomization within 2-methylpropane radical cations
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Derrick, P. J.↗
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Combustion problems of nitramine propellants
This study has, as its distinctive feature, a detailed examination of the condensed-phase processes in the combustion of nitramine propellants. As a consequence of a recently developed model for the combustion of ammonium perchlorate (AP)/composite propellants, it is hypothesized that the condensed-phase degradation of the nitramine oxidizer particles to a vaporizable state is the overall rate-limiting step. It is also assumed that the gas-phase details are secondary in importance and need be studied only to the extent of supplying the correct boundary conditions on the condensed-phase/vapor-phase heat transfer. Because of imprecise understanding of the gas-phase processes in the presence of combustion, several plausible models are considered for the gas phase. It is found that all of the gas-phase models considered lead to predictions sufficiently close to experimental trends to conclude that the precise details of gas-phase processes are not of critical importance in determining propellant combustion behavior.
Kumar, R. N.↗
Interstellar abundances - Gas and dust
Data on abundances of interstellar atoms, ions and molecules in front of zeta Oph are assembled and analyzed. The gas-phase abundances of at least 11 heavy elements are significantly lower, relative to hydrogen, than in the solar system. The abundance deficiencies of certain elements correlate with the temperatures derived theoretically for particle condensation in stellar atmospheres or nebulae, suggesting that these elements have condensed into dust grains near stars. There is evidence that other elements have accreted onto such grains after their arrival in interstellar space. The extinction spectrum of zeta Oph can be explained qualitatively and, to a degree, quantitatively by dust grains composed of silicates, graphite, silicon carbide, and iron, with mantles composed of complex molecules of H, C, N, and O. This composition is consistent with the observed gas-phase deficiencies.
Field, G. B.↗
Mechanism of ignition in shock wave interactions with reactive liquid droplets
A detailed qualitative analysis of the processes leading to the explosive ignition of a reactive liquid droplet that is suspended in a gas-phase oxidizer and subjected to the passage of a shock wave, is presented. The interval of time between shock wave passage and ignition is described by identifying a two-stage process which consists of a period of relative reactive dormancy that is followed by a chemical induction period leading to the thermal explosion of reactant that has been stripped from the liquid drop, vaporized, and mixed with the gas-phase oxidizer. The results of first-order calculations based on this model are presented and compared with experimental data for diethlcyclohexane drops in oxygen.
Pierce, T. H.↗
THERMAL DECOMPOSITION OF HYDRAZINE
The Thermal Stability of Hydrazine has been studied in the temperature and pressure intervals of 175" to 250"C. and 300 to 430 p.s.i., Respectively. Previous studies of the decomposition of hydrazine indicated that several factors affect its stability (2, 5, 7). the rate of decomposition is increased by the presence of certain surfaces (especially metals and salts). pH, oxygen, and carbon dioxide. Further explosive decomposition Is attributable to the uncontrolled heterogeneous, gas-phase decomposition. These factors were considered in selecting the following experimental conditions: highly purified hydrazine was prepared in a nitrogen atmosphere, and this product was decomposed over triply distilled mercury in outgassed borosilicate glass tubes at ullages that were initially zero. This study also included the effects of added quantities of ammonia on the rate of decomposition and an investigation of the products of the decomposition.
Harold W. Lucien↗
Liquid rocket combustion - An aerodynamically controlled process.
Liquid rocket propellant combustion processes covering liquid phase mixing, vaporization, spray formation, atomization, gas-phase mixing and chemical reaction
PROPELLANT COMBUSTION↗
High-pressure liquid-monopropellant strand combustion.
Examination of the influence of dissolved gases on the state of the liquid surface during high-pressure liquid-monopropellant combustion through the use of a strand burning experiment. Liquid surface temperatures were measured, using fine-wire thermocouples, during the strand combustion of ethyl nitrate, normal propyl nitrate, and propylene glycol dinitrate at pressures up to 81 atm. These measurements were compared with the predictions of a variable-property gas-phase analysis assuming an infinite activation energy for the decomposition reaction. The state of the liquid surface was estimated using a conventional low-pressure phase equilibrium model, as well as a high-pressure version that considered the presence of dissolved combustion-product gases in the liquid phase. The high-pressure model was found to give a superior prediction of measured liquid surface temperatures. Computed total pressures required for the surface to reach its critical mixing point during strand combustion were found to be in the range from 2.15 to 4.62 times the critical pressure of the pure propellant. Computed dissolved gas concentrations at the liquid surface were in the range from 35 to 50% near the critical combustion condition.
Faeth, G. M.↗
Oscillatory burning of solid propellants including gas phase time lag.
An analysis has been performed for oscillatory burning of solid propellants including gas phase time lag. The gaseous flame is assumed to be premixed and laminar with a one-step overall chemical reaction. The propellant is assumed to decompose according to the Arrenhius Law, with no condensed phase reaction. With this model, strong gas phase resonance has been found in certain cases at the characteristic gas-phase frequencies, but the peaking of the acoustic admittance is in the direction favoring the damping of pressure waves. At still higher frequencies, moderate wave-amplifying ability was found. The limit of low frequency response obtained previously by Denison and Baum was recovered, and the limitations of the quasi-steady theory were investigated.
T'Ien, J. S.↗
Photodetachment of electrons from amide and arsenide ions - The electron affinities of NH2., and AsH2.
The relative cross section for the gas-phase photodetachment of electrons has been determined for NH2(-) in the wavelength region of 1195 to 1695 nm and for AsH2(-) in the region from 620 to 1010 nm. An ion cyclotron resonance spectrometer was used to generate, trap, and detect negative ions. A 1000-W xenon arc lamp with a grating monochromator was used as the light source, except for one series of experiments in which a tunable laser was employed. Single sharp thresholds were observed in both cross sections, and the following electron affinity values were determined: 0.744 (plus or minus 0.022) eV for NH2. and 1.27 (plus or minus 0.03) eV for AsH2.
Smyth, K. C.↗
Control of Nitrogen Dioxide in Stack Emission by Reaction with Ammonia
The development of an acid base gas-phase reaction system which utilizes anhydrous ammonia as the reactant to remove nitrogen dioxide from hydrazine-nitrogen tetroxide rocket combustion exhaust is reported. This reaction reduced NO2 levels in exhaust emissions so that the resulting stack emission is completely white instead of the earlier observed typical reddish-brown coloration. Preliminary analyses indicate the importance of reaction time and ammonia concentration on removal efficiency and elimination of the health hazard to individuals with respiratory problems.
Metzler, A. J.↗
A new look at AP/composite propellant combustion
Some theoretical studies on the time-independent and oscillatory combustion of nonmetallized ammonium perchlorate (AP)/composite propellants are presented. A coherent and unified interpretation was made of the voluminous data available from experiments related to propellant combustion. Three fundamental hypotheses are introduced: the extent of propellant degradation at the vaporization step has to be specified through a scientific criterion; the condensed-phase degradation reaction of ammonium perchlorate to a vaporizable state is the overall rate-limiting step; gas-phase combustion rate is controlled by the mixing rate of fuel and oxidizer vapors. In the treatment of oscillatory combustion, the assumption of quasi-steady fluctuations in the gas phase is used to supplement these hypotheses.
Kumar, R. N.↗
Molecule formation in normal clouds
Some aspects of molecule formation in normal interstellar clouds, i.e., clouds having particle densities of less than 100 per cu cm, are discussed in light of recent studies. It is pointed out that, with their relatively large depletion parameter values (DPVs), CH clouds are 'young', whereas OH clouds have small DPVs and are 'old'. The theoretical reason for this is that OH, as a product of grain catalysis, persists over a much longer period of cloud evolution, whereas CH(+), CH, and CN, as products of gas-phase reaction, can be found only in 'young' clouds where depletion has not yet occurred. This may explain why OH has not been seen in radio observations of regions where CH(+), CH, and CN have been seen optically.
Aannestad, P. A.↗
Mass spectrometry
Review of the present status of mass spectrometry in the light of pertinent recent publications spanning the period from December 1971 to January 1974. Following an initial survey of techniques, instruments, and computer applications, a sharp distinction is made between the chemistry of organic (radical-)ions and analytical applications in biorganic chemistry and medicine. The emphasis is on the chemistry of organic (radical-)ions at the expense of inorganic, organometallic, and surface ion chemistry. Biochemistry and medicine are chosen because of their contemporary importance and because of the stupendous contributions of mass spectroscopy to these fields in the past two years. In the review of gas-phase organic ion chemistry, special attention is given to studies making significant contributions to the understanding of ion chemistry.
Burlingame, A. L.↗
Hot hydrogen in prebiological and interstellar chemistry
Two articles discuss the recent experimental work of Hong et al. on the production of amino acids and gas-phase organic compounds from the ultraviolet irradiation of simple gases, with hot hydrogen atoms used as the principal energy conversion agent. The reaction possibilities involving frozen ices are mentioned in both articles, as well as the significance of three-body collisions in this situation.
Sagan, C.↗
Open-loop response of a burning liquid monopropellant
A direct comparison was obtained between the theoretical and experimental response of a burning liquid monopropellant surface to imposed pressure oscillations. The comparison extended beyond the quasi-steady frequency regime into the range where the combustion process interacts with the thermal wave in the liquid phase. The theory considered both gas and liquid-phase transient effects, involving a numerically integrated, first-order perturbation analysis. The experiment employed hydrazine as the test fuel, burning as a strand. With kinetic parameters fixed by steady burning rate measurements, the model gave good predictions of liquid-phase temperature distributions during steady combustion as well as the amplitude and phase of the oscillatory component of the burning rate in the presence of imposed pressure oscillations. The combustion response tends to peak in two frequency ranges; one corresponding to interaction with liquid-phase transient effects, which could be verified both theoretically and experimentally; the second corresponding to gas-phase transient effects, which could only be examined theoretically. Both ranges provide conditions where the amplifying power is sufficient to drive combustion instability.
Allison, C. B.↗
Laboratory investigations: Low Earth orbit environment chemistry with spacecraft surfaces
Long-term space operations that require exposure of material to the low earth orbit (LEO) environment must take into account the effects of this highly oxidative atmosphere on material properties and the possible contamination of the spacecraft surroundings. Ground-based laboratory experiments at Los Alamos using a newly developed hyperthermal atomic oxygen (AO) source have shown that not only are hydrocarbon based materials effected but that inorganic materials such as MoS2 are also oxidized and that thin protective coatings such as Al2O3 can be breached, producing oxidation of the underlying substrate material. Gas-phase reaction products, such as SO2 from oxidation of MoS2 and CO and CO2 from hydrocarbon materials, have been detected and have consequences in terms of spacecraft contamination. Energy loss through gas-surface collisions causing spacecraft drag has been measured for a few select surfaces and has been found to be highly dependent on the surface reactivity.
Cross, Jon B.↗
The Effect of Gravity on the Combustion of Bulk Metals
In recent years, metal combustion studies at the University of Colorado have focused on the effects of gravity (g) on the ignition and burning behavior of bulk metals. The impetus behind this effort is the understanding of the ignition conditions and flammability properties of structural metals found in oxygen (O2) systems for space applications. Since spacecraft are subjected to higher-than-1g loads during launch and reentry and to a zero-gravity environment while in orbit, the study of ignition and combustion of bulk metals at different gravitational accelerations is of great practical concern. From the scientific standpoint, studies conducted under low gravity conditions provide simplified boundary conditions, since buoyancy is removed, and make possible the identification of fundamental ignition and combustion mechanisms. This investigation is intended to provide experimental verification of the influence of natural convection on the burning behavior of metals. In addition, the study offers the first findings of the influence of gravity on ignition of bulk metals and on the combustion mechanism and structure of metal-oxygen, vapor-phase diffusion flames in a buoyancy-free environment. Titanium (Ti) and magnesium (Mg) metals were chosen because of their importance as elements of structural materials and their simple chemical composition-pure metals instead of multicomponent alloys to simplify chemical and spectroscopic analyses. In addition, these elements present the two different combustion modes observed in metals: heterogeneous or surface burning (for Ti) and homogeneous or gas-phase reaction (for Mg). Finally, Mg, Ti, and their oxides exhibit a wide range of thermophysical and chemical properties. Metal surface temperature profiles, critical and ignition temperatures, propagation rates, burning times, and spectroscopic measurements are obtained under normal and reduced gravity. Visual evidence of all phenomena is provided by high-speed photography.
Branch, Melvyn C.↗
Effect of Surface Preparation and Gas Flow on Nitrogen Atom Surface Recombination
The effects of surface preparation and gas flow on the recombination of nitrogen atoms at copper and platinum surfaces were determined. Atoms were generated by an electrodeless 2450-megacycle-per-second discharge, and their concentration was measured by gas-phase titration with nitric oxide. Test surfaces were either vacuum-evaporated films or spheres machined from bulk metal and cemented around small glass-bead thermistors. Heat released by recombination was measured as the difference in electrical energy required to maintain a given thermistor temperature with and without a catalytic surface exposed. Recombination coefficients measured at flow velocities of 1120, 1790, 2250, and 3460 centimeters per second and at pressures of 0.42 and 0.59 millimeter of mercury showed that flow conditions had no effect. The results were also independent of atom concentration. A rough indication of the temperature dependence was obtained; it was greater for copper than for platinum. Platinum films deposited on platinum or on glass had the same activity - about 3 percent of the atoms impinging recombined. With copper, however, the glass substrate greatly reduced the percent of atoms recombining over that of a bulk copper substrate where 4 percent of the impinging atoms recombined. This effect could be overcome by depositing a second film on top of the first. Bulk metal samples were subjected to various surface treatments including polishing, degreasing with a chlorinated hydrocarbon, washing with nitric acid, and rinsing with water. Polished, degreased platinum had low activity compared to an evaporated film, but nitric acid treatment made it equivalent. Polished, degreased copper was only slightly less active than a copper film; nitric acid etching decreased the activity still further, probably by preferentially exposing facets of low catalytic efficiency.
Prok, George M.↗