Thermodynamic equilibria from plasma sources. III - Carbon-hydrogen-nitrogen systems
Product distribution of organic nitrogen compounds plasma sources computed by assuming high temperature limited thermodynamic equilibrium
SEARCH · Search NASA
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Product distribution of organic nitrogen compounds plasma sources computed by assuming high temperature limited thermodynamic equilibrium
Accurate vapor pressures are determined through direct weight loss measurements using the Knudsen effusion technique. The experimental data are evaluated by establishing the mode of vaporization and determining the heat capacity of cadmium selenide at elevated temperatures. Additional information is obtained through a second- and third-law evaluation of data, namely, the heat of formation and the absolute entropy of cadmium selenide. A preferential loss of selenium during the initial heating of CdSe is observed, which leads to a deviation in stoichiometry.
Simplified models were developed for radiative heating and cooling and for ozone photochemistry in the region 22-60 km. The latter permit the inclusion of nitrogen and hydrogen reactions in addition to simple oxygen reactions. The simplicity of the scheme facilitates the use of a wide variety of cooling and reaction rates. It is shown that joint radiative-photochemical equilibrium is appropriate to the mean state of the atmosphere between 35 and 60 km. The relaxation of perturbations from joint radiative-photochemical equilibrium was also investigated. In all cases the coupling between temperature dependent ozone photochemistry and radiation lead to a reduction of the thermal relaxation time from its purely radiative value. The latter, which amounts to about 10 days, is reduced to 2-4 days at heights of 31-35 km. This greatly enhances the dissipation of waves traveling through the stratosphere.
Explore the source record for details and available documents.
Let a rigid satellite move in a circular orbit about a spherically symmetric central body, taking into account only the main term of the gravitational torque. We investigate and find all solutions of the following problem. Let the satellite be permitted to spin about an axis that is fixed in the orbit frame; the satellite need not be symmetric, the spin not uniform, and the spin axis not a principal axis of inertia. The complete discussion of this type of spin reveals that the cases found by Lagrange and by Pringle - and the well-known spin about a principal axis of inertia orthogonal to the orbit plane - are essentially the only ones possible.
Pseudobrookite, is found in volcanic rocks, and the mineral armalcolite ((Fe,Mg)Ti2O5) found in the Apollo 11 and subsequent lunar samples seems to be unique to the moon. In plutonic rocks on the earth, ilmenite and rutile were found with what appears to be an equilibrium liquidus texture, while on the moon armalcolite often appears to be the primary liquidus phase among Ti-oxides. This suggests that total pressure may be a factor in the formation of these minerals, and a knowledge of the phase relations in this system yields information about the pressure under which a given magma crystallized.
Experiments on phase behavior in hydrogen-helium mixtures have been carried out at pressures up to 9.3 kilobars, at temperatures from 26 to 100 K. Two distinct fluid phases are shown to exist at supercritical temperatures and high pressures. Both the trend of the experimental results and an analysis based on the van der Waals theory of mixtures suggest that this fluid-fluid phase separation persists at temperatures and pressures beyond the range of these experiments, perhaps even to the limits of stability of the molecular phases. The results confirm earlier predictions concerning the form of the hydrogen-helium phase diagram in the region of pressure-induced solidification of the molecular phases at supercritical temperatures. The implications of this phase diagram for planetary interiors are discussed.
The determination of the relaxation time of a temperature perturbation in the stratosphere must take into account the effects of the absorption of solar energy by ozone, while the ozone density itself is dependent on temperature. A photochemical model, consisting of continuity equations for each of 29 constituents with reaction rates and adjustment times, is used to obtain the vertical distribution of ozone. The altitude range from 35 to 60 km in non-Arctic regions is shown to be in approximate joint radiative-photochemical equilibrium. The temperature and ozone distributions are thus well buffered. Modest changes in ozone and temperature were calculated on the basis of this model from large changes in cooling rates and reaction rates, and the results are shown to be more in line with actual observations. The importance of estimating the mixing ratios for NO and H2O is emphasized.
Explore the source record for details and available documents.
Titanate phase relations at liquidus temperatures are determined for the CaAl2Si2O8-Fe2TiO4-FeTi2O5 system in contact with metallic iron by reflected- and transmitted-light microscopy, electron microprobe, and X-ray diffraction analyses. Results of critical equilibration runs are presented, various primary phase areas and liquidus isotherms are illustrated, and the geometry of the system is described. Three piercing points are determined, and it is noted that the compositional interrelations among coexisting crystalline and liquid phases as well as the sequence of the various titanate phases are indicative of the significant effects of the various cations on the relative stability of these phases. It is found that Al2O3 exerts a strong stabilizing effect on the phase assemblage of ulvospinel plus ferropseudobrookite relative to ilemite.
Results of experiments investigating the crystallization of plagioclase from natural and synthetic melts are presented and are analyzed in terms of empirical and semiquantitative mixing models for the melt. Elemental partition constants were determined from the results and from other published data. Activities of the melt components were modeled by assuming that the melt consists of two independent quasi-lattices of network-forming and network-modifying components, each of which is an ideal solution of its respective component. The semiquantitative analysis supports the suggestion that Na(+) is strongly associated with tetrahedrally-coordinated Al in the melt. It is shown that it is possible to predict the composition of plagioclase crystallizing under equilibrium conditions from a dry melt of known composition and known temperature at low total pressure.
Explore the source record for details and available documents.
The paper studies the equilibrium of self-gravitating isothermal models of interstellar clouds with a frozen-in magnetic field linked smoothly to the field of a hot tenuous intercloud medium. Equilibrium states are determined which can be reached by clouds contracting nonhomologously from a spherical uniform initial state. Three free parameters characterize the problem: a dimensionless initial radius related to the Jeans length of the cloud, the initial ratio of the magnetic and gas pressures in the cloud, and the initial ratio of the intercloud and cloud pressures. The dependence of the solutions on each of these parameters is investigated. It is found that: (1) the frozen-in field causes the cloud to become oblate with its major axis normal to the field lines; (2) the flattening increases as the magnetic-field strength, gravitational forces, or intercloud pressure increases; (3) increasing intercloud pressure eventually leads to gravitational collapse; and (4) the cloud can reach equilibrium only if its radius does not exceed some critical value. The observed inefficiency of the star-formation process within massive clouds is examined and explained in terms of magnetic phenomena in a collapsing cloud.
Phase diagrams for two-phase solids and eutectic, monotectic, peritectic, and syntectic reactions in low gravity applications to processes and products are considered.
Experimental crystallization of a lunar picrite composition (sample 12002) at controlled linear cooling rates produces systematic changes in the temperature at which crystalline phases appear, in the texture, and in crystal morphology as a function of cooling rate. Phases crystallize in the order olivine, chromium spinel, pyroxene, plagioclase, and ilmenite during equilibrium crystallization, but ilmenite and plagioclase reverse their order of appearance and silica crystallizes in the groundmass during controlled cooling experiments. The partition of iron and magnesium between olivine and liquid is independent of cooling rate, temperature, and pressure. Comparison of the olivine nucleation densities in the lunar sample and in the experiments indicates that the sample began cooling at about 1 deg C/hr. Pyroxene size, chemistry, and growth instability spacings, as well as groundmass coarseness, all suggest that the cooling rate subsequently decreased by as much as a factor of 10 or more. The porphyritic texture of this sample, then, is produced at a decreasing, rather than a discontinuously increasing, cooling rate.
Potassium has been found to have extremely limited absolute solubility in Fe-S liquid in the pressure-temperature range of 18 to 40 kbars, 1050 to 1150 C, and fO2 within the field of metallic iron. It also partitioned into a certain silicate phase highly in preference to Fe-S liquid at 30 kbar and 1100 C. The dependence of the partitioning of K between solid silicate and Fe-S liquid on fO2 and compositions of mineral solid solutions have been analyzed. These experimental data, along with those of others, limit the amount of K that could fractionate in Fe-S liquid layers or a core in the early history of the moon and, thus, act as localized heat sources in its thermal history models; the data also seem to argue against a chondritic abundance of potassium for earth. The question of fractionation of enough K-40 in an Fe-S liquid outer core of earth to provide the necesary thermal energy for the geomagnetic dynamo remains unresolved.
Experimental studies were made on the compositional dependence of the redox equilibrium of Eu in synthetic silicate liquids, together with an empirical model describing the observed compositional dependence. Electron paramagnetic resonance (EPR) was used to measure the concentration ratio of Eu(2+) to Eu(3+) in various glasses formed by rapidly quenching silicate liquids. The compositional field studied comprised mixtures of SiO2, TiO2, Al2O3, CaO, MgO, and Na2O. The proposed model describes the Eu(2+)/Eu(3+) ratio over the entire compositional field in terms of parameters easily related to each glass composition. The general applicability and utility of the model is further demonstrated by its application to the Fe(2+)-Fe(3+), Ce(3+)-Ce(4+), and Cr(3+)-Cr(6+) redox reactions in binary alkali oxide silicate glasses of Li, Na, and K.
Bernstein, Greene, and Kruskal (1957) showed how, given the electrostatic potential as a function of position, the entire distribution function for ions, and the distribution function for untrapped electrons in a one-dimensional two-species Vlasov plasma, one could determine the distribution function for the trapped electrons as the solution of an Abel integral equation. This result is generalized by replacing the statements about the distribution functions with the specification of the velocity-space distribution functions of both species at a single position in the plasma. Limiting cases are shown to correspond to the earlier treatment, and the applicability of the theory to experiment is discussed.