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NASA NTRS1982

Crude oil desulfurization

High sulfur crude oil is desulfurized by a low temperature (25-80 C.) chlorinolysis at ambient pressure in the absence of organic solvent or diluent but in the presence of water (water/oil=0.3) followed by a water and caustic wash to remove sulfur and chlorine containing reaction products. The process described can be practiced at a well site for the recovery of desulfurized oil used to generate steam for injection into the well for enhanced oil recovery.

Kalvinskas, J. J.↗

NASA NTRS1982

Origin of rims on coarse-grained inclusions in the Allende meteorite

Coarse-grained, calcium-rich inclusions in the Allende meteorite are enclosed by sequences of very thin, mineralogically distinct rim layers. A number of questions arise in connection with the presence of rims. The present investigation presents new observations bearing on all these questions and provides a model for the formation of rims. A zoned alteration vein is considered along with a sinuous inclusion, a spinel-perovskite-melilite band (SP), layers overlying the melilite-rich side of SP, a layer overlying the spinel-rich side of SP, and aspects of rim composition and the degree of alteration in coarse-grained inclusions. It is proposed that rims on coarse-grained inclusions formed in a nonequilibrium process involving those reactions between coarse-grained melilite and spinel and a nebular gas phase which also produced the secondary alteration products in the interiors of these inclusions.

Macpherson, G. J.↗

NASA NTRS1983

Photochemistry of N2(+) in the daytime F region

The photochemistry of N2(+) in the daytime F region continues to be a source of concern due primarily to the uncertain roles of the metastable O+(2D) ion and possible vibrational excitation. This investigation adopts a unique subset of data from the Atmospheric Explorer C satellite that spans distinct regions near the low-latitude F peak wherein either chemical reactions or electron processes alternatively control the N2(+) abundances. Concentrations of N2(+) calculated according to current theory and including recent laboratory data for O+(2D) losses via N2 are found to exceed ionospheric observations between 220 and 400 km by a factor near 2. Relevant characteristics of the basic molecular ion concentration measurements are described, along with an analysis for select orbits conducted according to current photochemical equilibrium theory. Possible simple modifications of this theory are discussed in terms of the constraints suggested by the nature of the observations.

Breig, E. L.↗

NASA NTRS1985

Nitrogen species

Total odd nitrogen, NO(y), may be defined as the sum of all active nitrogen species that interchange photochemically with one another on a time scale of the order of weeks or less. As noted, NO + NO2 reactions dominate the processes controlling the ozone balance in the contemporary stratosphere. The observational data from non-satellite platforms are reviewed. The growth in available satellite data in the past four years is considered. Some of the most important scientific issues are discussed, taking into account new results from atmospheric models (mainly 2-D). The model results are compared with the observational data.

Harries, J. E.↗

NASA NTRS1986

Effects of varying environmental parameters on trace contaminant concentrations in the NASA Space Station Reference Configuration

An evaluation is made of the NASA Space Station Reference Configuration trace contaminant production and depletion level effects of CO2, O2, humidity, temperature, and pressure variations, on the basis of a computer model of the Reference Configuration's chemical reactions and physical processes as functions of time. The effects of changes in the initial concentrations of such contaminants as nonmethane hydrocarbons and nitrogen oxides are also examined, and these are found to result in more significant changes in the concentration levels of trace contaminants than pressure and humidity variations. O2 and CO2 changes are found to have negligible effects on trace contaminant concentrations.

Brewer, Dana A.↗

NASA NTRS1988

Computed potential energy surfaces for chemical reactions

The minimum energy path for the addition of a hydrogen atom to N2 is characterized in CASSCF/CCI calculations using the (4s3p2d1f/3s2p1d) basis set, with additional single point calculations at the stationary points of the potential energy surface using the (5s4p3d2f/4s3p2d) basis set. These calculations represent the most extensive set of ab initio calculations completed to date, yielding a zero point corrected barrier for HN2 dissociation of approx. 8.5 kcal mol/1. The lifetime of the HN2 species is estimated from the calculated geometries and energetics using both conventional Transition State Theory and a method which utilizes an Eckart barrier to compute one dimensional quantum mechanical tunneling effects. It is concluded that the lifetime of the HN2 species is very short, greatly limiting its role in both termolecular recombination reactions and combustion processes.

Walch, Stephen P.↗

NASA NTRS1990

Design of a lunar oxygen production plant

To achieve permanent human presence and activity on the moon, oxygen is required for both life support and propulsion. Lunar oxygen production using resources existing on the moon will reduce or eliminate the need to transport liquid oxygen from earth. In addition, the co-products of oxygen production will provide metals, structural ceramics, and other volatile compounds. This will enable development of even greater self-sufficiency as the lunar outpost evolves. Ilmenite is the most abundant metal-oxide mineral in the lunar regolith. A process involving the reaction of ilmenite with hydrogen at 1000 C to produce water, followed by the electrolysis of this water to provide oxygen and recycle the hydrogen has been explored. The objective of this 1990 Summer Faculty Project was to design a lunar oxygen-production plant to provide 5 metric tons of liquid oxygen per year from lunar soil. The results of this study describe the size and mass of the equipment, the power needs, feedstock quantity and the engineering details of the plant.

Radhakrishnan, Ramalingam↗

NASA NTRS1992

Organic crystal growth experiment facility (13-IML-1)

The interesting nature of metal-like organic compounds composed of charge transfer complexes has been recently realized. Crystals of these complexes can usually be grown by the solution crystallization method. It is difficult to grow such organic crystals on Earth, especially from the chemical reactions through diffusion controlled process in the solutions, because of gravitational disturbances, or sedimentation. The International Microgravity Lab. (IML-1) Organic Crystal Growth with G-Gitter Preventive Measure (OCGP) experiment is expected to grow a single crystal large enough to allow its intrinsic physical properties to be measured and its detailed crystal structure to be determined. This experiment also attempts to assess the experimental conditions including the microgravity environment for further study of the fundamental process of solution crystallization, nucleation, and growth from supersaturated phases including chemical reactions. Microgravity disturbances, G-jitter, may be an important environmental factor in the experimental method to assess. The vibration damping effects on organic crystal growth can be carefully studied.

Kanbayashi, Akio↗

NASA NTRS1991

A continuous mixing model for pdf simulations and its applications to combusting shear flows

The problem of time discontinuity (or jump condition) in the coalescence/dispersion (C/D) mixing model is addressed in this work. A C/D mixing model continuous in time is introduced. With the continuous mixing model, the process of chemical reaction can be fully coupled with mixing. In the case of homogeneous turbulence decay, the new model predicts a pdf very close to a Gaussian distribution, with finite higher moments also close to that of a Gaussian distribution. Results from the continuous mixing model are compared with both experimental data and numerical results from conventional C/D models.

Hsu, A. T.↗

NASA NTRS1992

PDF turbulence modeling and DNS

The problem of time discontinuity (or jump condition) in the coalescence/dispersion (C/D) mixing model is addressed in probability density function (pdf). A C/D mixing model continuous in time is introduced. With the continuous mixing model, the process of chemical reaction can be fully coupled with mixing. In the case of homogeneous turbulence decay, the new model predicts a pdf very close to a Gaussian distribution, with finite higher moments also close to that of a Gaussian distribution. Results from the continuous mixing model are compared with both experimental data and numerical results from conventional C/D models. The effect of Coriolis forces on compressible homogeneous turbulence is studied using direct numerical simulation (DNS). The numerical method used in this study is an eight order compact difference scheme. Contrary to the conclusions reached by previous DNS studies on incompressible isotropic turbulence, the present results show that the Coriolis force increases the dissipation rate of turbulent kinetic energy, and that anisotropy develops as the Coriolis force increases. The Taylor-Proudman theory does apply since the derivatives in the direction of the rotation axis vanishes rapidly. A closer analysis reveals that the dissipation rate of the incompressible component of the turbulent kinetic energy indeed decreases with a higher rotation rate, consistent with incompressible flow simulations (Bardina), while the dissipation rate of the compressible part increases; the net gain is positive. Inertial waves are observed in the simulation results.

Hsu, A. T.↗

NASA NTRS1993

The spectral effects of subsolidus reduction of olivine and pyroxene

The surfaces of atmosphereless bodies are subjected to a variety of chemical, thermal, accretionary, and shock processes related to their regolith environment. These processes are responsible for a number of alterations that occur in regoliths. Alterations include particle size commutation, implantation of solar wind gases, formation of agglutinates, spectral darkening, and, in the lunar case, the development of the very strong red continuum slope in the visible and near infrared spectra. A great deal of work has pointed to the role of agglutinates as the principal agent for darkening and reddening the lunar soil. The measures of regolith maturity are strongly linked to the accumulation of agglutinates. Recent work has suggested that the finest fractions of agglutinitic glass are major source of the spectral red slope. In particular, the red slope is most strongly associated with the agglutinitic glasses that are rich in blebs of sub-micron sized metal particles. It is thought that these metal particles, because of their size and scattering efficiently relative to the wavelength of light, are responsible for the red continuum slope. This fine fraction of metal particles is produced primarily by reduction of Fe(+2) from silicates. One mechanism for the reduction process is the reaction of solar implanted wind protons with the regolith soil during impact events. In this case the presence of hydrogen creates a reducing environment and the thermal pulse from the impact greatly speeds the reaction kinetics. To explore other reducing and thermal environments a series of experiments were done using samples in evacuated capsules buffered by Tantalum and heated to subsolidus temperatures.

Britt, D. T.↗

NASA NTRS1996

Template-Directed Ligation of Peptides to Oligonucleotides

Synthetic oligonucleotides and peptides have enjoyed a wide range of applications in both biology and chemistry. As a consequence, oligonucleotide-peptide conjugates have received considerable attention, most notably in the development of antisense constructs with improved pharmacological properties. In addition, oligonucleotide-peptide conjugates have been used as molecular tags, in the assembly of supramolecular arrays and in the construction of encoded combinatorial libraries. To make these chimeric molecules more accessible for a broad range of investigations, we sought to develop a facile method for joining fully deprotected oligonucleotides and peptides through a stable amide bond linkage. Furthermore, we wished to make this ligation reaction addressable, enabling one to direct the ligation of specific oligonucleotide and peptide components.To confer specificity and accelerate the rate of the reaction, the ligation process was designed to be dependent on the presence of a complementary oligonucleotide template.

Bruick, Richard K.↗

NASA NTRS1998

Structure of Flame Balls at Low Lewis-Number (SOFBALL): Preliminary Results From the STS-83 and STS-94 Space Flight Experiments

Results from the Structure Of Flame Balls At Low Lewis-number (SOFBALL) space flight experiment conducted on the MSL-1 Space Shuttle missions are reported. Several new insights were obtained, including: much lower buoyancy-induced drift speed than anticipated pre-flight; repulsion of adjacent flame balls due to their mutual interaction; remarkable sensitivity of flame balls to small accelerations resulting from Orbiter attitude control maneuvers; and very similar net heat release for all flame balls in all mixtures tested. Comparison of experimental results to computational predictions reveals limitations in current models of H2-02 chemistry for very lean mixtures. It is discussed how the results of these space experiments may provide an improved understanding of the interactions of the two most important phenomena in combusting materials, namely chemical reaction and transport processes, in the unequivocally simplest possible configuration.

Ronney, Paul D.↗

NASA NTRS2001

Thermodynamic Activity Measurements with Knudsen Cell Mass Spectrometry

Coupling the Knudsen effusion method with mass spectrometry has proven to be one of the most useful experimental techniques for studying the equilibrium between condensed phases and complex vapors. The Knudsen effusion method involves placing a condensed sample in a Knudsen cell, a small "enclosure", that is uniformly heated and held until equilibrium is attained between the condensed and vapor phases. The vapor is continuously sampled by effusion through a small orifice in the cell. A molecular beam is formed from the effusing vapor and directed into a mass spectrometer for identification and pressure measurement of the species in the vapor phase. Knudsen cell mass spectrometry (KCMS) has been used for nearly fifty years now and continues to be a leading technique for obtaining thermodynamic data. Indeed, much of the well-established vapor specie data in the JANAF tables has been obtained from this technique. This is due to the extreme versatility of the technique. All classes of materials can be studied and all constituents of the vapor phase can be measured over a wide range of pressures (approximately 10(exp -4) to 10(exp -11) bar) and temperatures (500-2800 K). The ability to selectively measure different vapor species makes KCMS a very powerful tool for the measurement of component activities in metallic and ceramic solutions. Today several groups are applying KCMS to measure thermodynamic functions in multicomponent metallic and ceramic systems. Thermodynamic functions, especially component activities, are extremely important in the development of CALPHAD (Calculation of Phase Diagrams) type thermodynamic descriptions. These descriptions, in turn, are useful for modeling materials processing and predicting reactions such as oxide formation and fiber/matrix interactions. The leading experimental methods for measuring activities are the Galvanic cell or electro-motive force (EMF) technique and the KCMS technique. Each has specific advantages, depending on material and conditions. The EMF technique is suitable for lower temperature measurements, provided a suitable cell can be constructed. KCMS is useful for higher temperature measurements in a system with volatile components. In this paper, we briefly review the KCMS technique and identify the major experimental issues that must be addressed for precise measurements. These issues include temperature measurements, cell material and cell design and absolute pressure calibration. The resolution of these issues are discussed together with some recent examples of measured thermodynamic data.

Copland, Evan H.↗

NASA NTRS1999

Advanced Microscopic Integrated Thermocouple Arrays

The purpose of this research is to develop and refine a technique for making microscopic thermocouple arrays for use in measuring the temperature gradient across a solid-liquid interface during the solidification process. Current thermocouple technology does not allow for real-time measurements across the interface due to the prohibitive size of available thermocouples. Microscopic thermocouple arrays will offer a much greater accuracy and resolution of temperature measurements across the solid-liquid interface which will lead to a better characterization of the solidification process and interface reaction which affect the properties of the resulting material.

Pettigrew, Penny J.↗

NASA NTRS2004

Searching for an Acidic Aquifer in the Rio Tinto Basin: First Geobiology Results of MARTE Project

Among the conceivable modern habitats to be explored for searching life on Mars are those potentially developed underground. Subsurface habitats are currently environments that, under certain physicochemical circumstances, have high thermal and hydrochemical stability [1, 2]. In planets like Mars lacking an atmospheric shield, such systems are obviously protected against radiation, which strongly alters the structure of biological macromolecules. Low porosity but fractured aquifers currently emplaced inside ancient volcano/sedimentary and hydrothermal systems act as excellent habitats [3] due to its thermal and geochemical properties. In these aquifers the temperature is controlled by a thermal balance between conduction and advection processes, which are driven by the rock composition, geological structure, water turnover of aquifers and heat generation from geothermal processes or chemical reactions [4]. Moreover, microbial communities based on chemolithotrophy can obtain energy by the oxidation of metallic ores that are currently associated to these environments. Such a community core may sustain a trophic web composed of non-autotrophic forms like heterotrophic bacteria, fungi and protozoa.

Fernandez-Remolar, D. C.↗

NASA NTRS2004

Structure of Flame Balls at Low Lewis-Number (SOFBALL): New Results from STS-107

Experiments on steady, spherically-symmetric premixed-gas flames ("flame balls") performed on STS-107 are described. These experiments were motivated by results obtained on earlier Space Shuttle missions. The motivation and objectives for the STS-107 experiments are described, along with the results obtained. Among the highlights of STS-107 were the weakest flames ever burned either on earth or in space (about 0.5 Watt of heat release), the leanest flames ever burned either on earth or in space, and the longest-lived flame ever burned in space. While many of the questions left unresolved from the earlier space flights were answered, some new and as yet unexplained phenomena were found, for example flame balls migrating in spiral patterns. Nonetheless, flame ball experiments have provided an insight into the interactions of the two most important phenomena in combusting materials, namely chemical reaction and transport processes, in the unequivocally simplest possible configuration.

Abid, Mohamed↗

NASA NTRS2000

Changing genetic information through RNA editing

RNA editing, the post-transcriptional alteration of a gene-encoded sequence, is a widespread phenomenon in eukaryotes. As a consequence of RNA editing, functionally distinct proteins can be produced from a single gene. The molecular mechanisms involved include single or multiple base insertions or deletions as well as base substitutions. In mammals, one type of substitutional RNA editing, characterized by site-specific base-modification, was shown to modulate important physiological processes. The underlying reaction mechanism of substitutional RNA editing involves hydrolytic deamination of cytosine or adenosine bases to uracil or inosine, respectively. Protein factors have been characterized that are able to induce RNA editing in vitro. A supergene family of RNA-dependent deaminases has emerged with the recent addition of adenosine deaminases specific for tRNA. Here we review the developments that have substantially increased our understanding of base-modification RNA editing over the past few years, with an emphasis on mechanistic differences, evolutionary aspects and the first insights into the regulation of editing activity.

Review↗