Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Chemical Reaction Cycle”

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.

At least 37 records · Page 2

Status of the DOE (STOR)-sponsored national program on hydrogen production from water via thermochemical cycles

The program structure is presented. The activities of the thermochemical cycles program are grouped according to the following categories: (1) specific cycle development, (2) support research and technology, (3) cycle evaluation. Specific objectives and status of on-going activities are discussed. Chemical reaction series for the production of hydrogen are presented. Efficiency and economic evaluations are also discussed.

Baker, C. E.↗

Chamber for Simulating Martian and Terrestrial Environments

An apparatus for simulating the environment at the surface of Mars has been developed. Within the apparatus, the pressure, gas composition, and temperature of the atmosphere; the incident solar visible and ultraviolet (UV) light; and the attenuation of the light by dust in the atmosphere can be simulated accurately for any latitude, season, or obliquity cycle over the entire geological history of Mars. The apparatus also incorporates instrumentation for monitoring chemical reactions in the simulated atmosphere. The apparatus can be used for experiments in astrobiology, geochemistry, aerobiology, and aerochemistry related to envisioned robotic and human exploration of Mars. Moreover, the apparatus can be easily adapted to enable similar experimentation under environmental conditions of (1) the surfaces of moons, asteroids, and comets, and (2) the upper atmospheres of planets other than Mars: in particular, it can be made to simulate conditions anywhere in the terrestrial atmosphere at altitudes up to about 100 km.

Schuerger, Andrew C.↗

The origin of intermediary metabolism

The core of intermediary metabolism in autotrophs is the citric acid cycle. In a certain group of chemoautotrophs, the reductive citric acid cycle is an engine of synthesis, taking in CO(2) and synthesizing the molecules of the cycle. We have examined the chemistry of a model system of C, H, and O that starts with carbon dioxide and reductants and uses redox couples as the energy source. To inquire into the reaction networks that might emerge, we start with the largest available database of organic molecules, Beilstein on-line, and prune by a set of physical and chemical constraints applicable to the model system. From the 3.5 million entries in Beilstein we emerge with 153 molecules that contain all 11 members of the reductive citric acid cycle. A small number of selection rules generates a very constrained subset, suggesting that this is the type of reaction model that will prove useful in the study of biogenesis. The model indicates that the metabolism shown in the universal chart of pathways may be central to the origin of life, is emergent from organic chemistry, and may be unique.

Non-NASA Center↗

Searching for Biogeochemical Cycles on Mars

The search for life on Mars clearly benefits from a rigorous, yet broad, definition of life that compels us to consider all possible lines of evidence for a martian biosphere. Recent studies in microbial ecology illustrate that the classic definition of life should be expanded beyond the traditional definition of a living cell. The traditional defining characteristics of life are threefold. First, life is capable of metabolism, that is, it performs chemical reactions that utilize energy and also synthesize its cellular constituents. Second, life is capable of self-replication. Third, life can evolve in order to adapt to environmental changes. An expanded, ecological definition of life also recognizes that life is a community of organisms that must interact with their nonliving environment through processes called biogeochemical cycles. This regenerative processing maintains, in an aqueous conditions, a dependable supply of nutrients and energy for growth. In turn, life can significantly affect those processes that control the exchange of materials between the atmosphere, ocean, and upper crust. Because metabolic processes interact directly with the environment, they can alter their surroundings and thus leave behind evidence of life. For example, organic matter is produced from single-carbon-atom precursors for the biosynthesis of cellular constituents. This leads to a reservoir of reduced carbon in sediments that, in turn, can affect the oxidation state of the atmosphere. The harvesting of chemical energy for metabolism often employs oxidation-reduction reactions that can alter the chemistry and oxidation state of the redox-sensitive elements carbon, sulfur, nitrogen, iron, and manganese. Have there ever been biogeochemical cycles on Mars? Certain key planetary processes can offer clues. Active volcanism provides reduced chemical species that biota can use for organic synthesis. Volcanic carbon dioxide and methane can serve as greenhouse gases. Thus the persistence of volcanism on Mars may well have influenced the persistence of a martian biosphere. The geologic processing of the crust can affect the availability of nutrients and also control the deposition of minerals that could have served as a medium for the preservation of fossil information. Finally, the activity of liquid water is crucial to life. Was there ever an Earth-like hydrologic cycle with rainfall? Has aqueous activity instead been restricted principally to hydrothermal activity below the surface? To what extent did the inorganic chemistry driven by sunlight and hydrothermal activity influence organic chemistry (prebiotic chemical evolution)? This paper addresses these and other key questions.

DesMarais, David J.↗

Chemical Weathering Kinetics of Basalt on Venus

The purpose of this project was to experimentally measure the kinetics for chemical weathering reactions involving basalt on Venus. The thermochemical reactions being studied are important for the CO2 atmosphere-lithosphere cycle on Venus and for the atmosphere-surface reactions controlling the oxidation state of the surface of Venus. These reactions include the formation of carbonate and scapolite minerals, and the oxidation of Fe-bearing minerals. These experiments and calculations are important for interpreting results from the Pioneer Venus, Magellan, Galileo flyby, Venera, and Vega missions to Venus, for interpreting results from Earth-based telescopic observations, and for the design of new Discovery class (e.g., VESAT) and New Millennium missions to Venus such as geochemical landers making in situ elemental and mineralogical analyses, and orbiters, probes and balloons making spectroscopic observations of the sub-cloud atmosphere of Venus.

Fegley, Bruce, Jr.↗

Researches on Preliminary Chemical Reactions in Spark-Ignition Engines

Chemical reactions can demonstrably occur in a fuel-air mixture compressed in the working cylinder of an Otto-cycle (spark ignition) internal-combustion engine even before the charge is ignited by the flame proceeding from the sparking plug. These are the so-called "prelinminary reactions" ("pre-flame" combustion or oxidation), and an exact knowledge of their characteristic development is of great importance for a correct appreciation of the phenomena of engine-knock (detonation), and consequently for its avoidance. Such reactions can be studied either in a working engine cylinder or in a combustion bomb. The first method necessitates a complicated experimental technique, while the second has the disadvantage of enabling only a single reaction to be studied at one time. Consequently, a new series of experiments was inaugurated, conducted in a motored (externally-driven) experimental engine of mixture-compression type, without ignition, the resulting preliminary reactions being detectable and measurable thermometrically.

Muehlner, E.↗

Future aircraft and potential effects on stratospheric ozone and climate

Initial studies with LLNL models of global atmospheric chemical, radiative, and transport processes have indicated that substantial decreases in stratospheric ozone concentrations could result from emissions of NO(x) from aircraft flying in the stratosphere, depending on fleet size and magnitude of the engine emissions. These studies used homogeneous chemical reaction rates (e.g., gas-phase chemistry). Recent evidence indicates that reactions on particles in the stratosphere may be important. Heterogeneous chemical reactions convert NO(x) (NO and NO2) molecules to HNO3. This decreases the odd oxygen loss from the NO(x) catalytic cycle and increases the odd oxygen loss from the Cl(x) catalytic cycle. By including these heterogeneous reactions in the LLNL model, the relative partitioning of odd oxygen loss between these two families changes, with the result that emissions of NO(x) from proposed aircraft fleets flying in the stratosphere now increase ozone. Having these heterogeneous processes present also increases ozone concentration in the troposphere relative to gas-phase only chemistry calculations for emissions of NO(x) from subsonic aircraft.

Kinnison, Douglas E.↗

A preliminary sensitivity analysis of the coupled diffusion and chemistry model

The sensitivity of the coupled chemistry/diffusion model's outputs to a wide range of variation of the model's independent variables has been investigated. It is shown that the efficiency with which the now catalytic cycle destroys ambient O3 is extremely sensitive to the amount of NO emitted and to the relative rates of turbulent diffusion and chemical reactions. For representative conditions in the stratosphere, a tenfold variation of either the turbulence intensity or the reaction rate constant or the source strength can vary the efficiency from 1% to 50%. If the duration of Phase 3 is a significant fraction of the total residence time of the plume, then these efficiency variations can alter O3 depletion rates by more than a factor of two. These results, therefore, point toward those variables which must be accurately defined or measured if one is to adequately predict the effect of SST operations on the ambient inventory of O3 in the lower stratosphere.

Hilst, G. R.↗

Stability and photochemistry of ClO dimers formed at low temperature in the gas phase

The recent observations of elevated concentrations of the ClO radical in the austral spring over Antarctica have implicated catalytic destruction by chlorine in the large depletions seen in the total ozone column. One of the chemical theories consistent with an elevated concentration of the ClO is a cycle involving the formation of the ClO dimer through the association reaction: ClO + ClO = Cl2O2 and the photolysis of the dimer to give the active Cl species necessary for O3 depletion. Here, researchers report experimental studies designed to characterize the dimer of ClO formed by the association reaction at low temperatures. ClO was produced by static photolysis of several different precursor systems: Cl sub 2 + O sub 3; Cl sub 2 O sub 2; OClO + Cl sub 2 O spectroscopy in the U.V. region, which allowed the time dependence of Cl sub 2, Cl sub 2 O, ClO, OClO, O sub 3 and other absorbing molecules to be determined.

Cox, R. A.↗

Some analyses of the chemistry and diffusion of SST exhaust materials during phase 3 of the wake period

In the generally stably stratified lower stratosphere, SST exhaust plumes could spend a significant length of time in a relatively undispersed state. This effort has utilized invariant modeling techniques to simulate the separate and combined effects of atmospheric turbulence, turbulent diffusion, and chemical reactions of SST exhaust materials in the lower stratosphere. The primary results to date are: (1) The combination of relatively slow diffusive mixing and rapid chemical reactions during the Phase III wake period minimizes the effect of SST exhausts on O3 depletion by the so-called NOx catalytic cycle. While the SST-produced NO is substantially above background concentrations, it appears diffusive mixing of NO and O3 is simply too slow to produce the O3 depletions originally proposed. (2) The time required to dilute the SST exhaust plume may be a significant fraction of the total time these materials are resident in the lower stratosphere. If this is the case, then prior estimates of the environmental impact of these materials must be revised significantly downward.

Hilst, G. R.↗

The rate of chemical weathering of pyrite on the surface of Venus

This abstract reports results of an experimental study of the chemical weathering of pyrite (FeS2) under Venus-like conditions. This work, which extends the earlier study by Fegley and Treiman, is part of a long range research program to experimentally measure the rates of thermochemical gas-solid reactions important in the atmospheric-lithospheric sulfur cycle on Venus. The objectives of this research are (1) to measure the kinetics of thermochemical gas-solid reactions responsible for both the production (e.g., anhydrite formation) and destruction (e.g., pyrrhotite oxidation) of sulfur-bearing minerals on the surface of Venus and (2) to incorporate these and other constraints into holistic models of the chemical interactions between the atmosphere and surface of Venus. Experiments were done with single crystal cubes of natural pyrite (Navajun, Logrono, Spain) that were cut and polished into slices of known weight and surface area. The slices were isothermally heated at atmospheric pressure in 99.99 percent CO2 (Coleman Instrument Grade) at either 412 C (685 K) or 465 C (738 K) for time periods up to 10 days. These two isotherms correspond to temperatures at about 6 km and 0 km altitude, respectively, on Venus. The reaction rate was determined by measuring the weight loss of the reacted slices after removal from the furnace. The reaction products were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy on the SEM.

Fegley, B., Jr.↗

Development of energy-absorbing reaction-sintered Si3N4 surface layers on hot-pressed Si3N4

Energy-absorbing Si3N4 surface layers on dense Si3N4 substrates were formed by in-place nitridation of fine-grained silicon powder. Ballistic impact tests performed on samples with 1-mm thick layers at room temperature and 1370 C showed up to an eightfold increase in the energy necessary to fracture the substrate. For maximum impact resistance, a small amount (about 20 vol %) of residual Si must be present in the reaction-sintered Si3N4 surface layer. Thermal cycling to 1370 C did not affect impact resistance, even though a considerable amount of SiO2 formed within the reaction-sintered Si3N4 layer during cycling. Erosion testing of samples in a Mach 0.8 burner rig at 1370 C resulted in minimal surface recession of the surface layer. Chemically vapor-deposited SiC-coated material similarly tested exhibited no surface recession.

Brennan, J. J.↗

The global troposphere - Biogeochemical cycles, chemistry, and remote sensing

The chemical composition of the troposphere is controlled by various biogeochemical cycles that couple the atmosphere with the oceans, the solid earth and the biosphere, and by atmospheric photochemical/chemical reactions. These cycles and reactions are discussed and a number of key questions concerning tropospheric composition and chemistry for the carbon, nitrogen, oxygen and sulfur species are identified. Next, various remote sensing techniques and instruments capable of measuring and monitoring tropospheric species from the ground, aircraft and space to address some of these key questions are reviewed. Future thrusts in remote sensing of the troposphere are also considered.

Levine, J. S.↗

Enhanced hydrophilicity of chlorided aluminum oxide particulates

An enhancement of hydrophilicity for chlorided aluminas was demonstrated by the results obtained from gaseous H2O sorptions at 70-, 80-, and 86-percent relative humidity on alpha and gamma aluminum oxide particulates and on alpha and gamma aluminum oxide particulates with a chemisorbed surface chloride phase (produced by reactions of gaseous HCl + H2O on alumina). Continuous sorption histories for H2O on chlorided aluminas having specific surface areas that range from 7 to 227 sq m/g before chloriding indicated that initial sorption rates were directly linked to the extent of chemisorbed chlorided coverage and implied the same relationship for sorption capacities. The initial sorption rate on chlorided aluminas was found to be slower for the first exposure to H2O than for subsequent exposures (which reached equilibrated H2O coverages much faster), suggesting that slow chemical reactions between H2O and chlorided alumina may have been operative during initial exposures. Chlorided alumina particles were found to remain very hydrophilic (relative to nonchlorided analogs) for several H2O sorption/desorption cycles.

Cofer, W. R., III↗

Mg2Si As Li-Intercalation Host For Li Cells

Compound Mg2Si shows promise as lithium-intercalation host for ambient-temperature rechargeable lithium electrochemical cells. As anode reactant material, LiXMg2Si chemically stable in presence of organic electrolyte used in such cells and stores large amounts of lithium. Intercalation reactions highly reversible at room temperature. Also retains sufficient mechanical strength during charge/discharge cycling. Lithium cells containing LixMg2Si anodes prove useful in spacecraft, military, communications, automotive, and other applications in which high energy-storage densities of lithium cells in general and rechargeability of cells needed.

Huang, Chen-Kuo↗

Low-cost solar array project task 1: Silicon material. Gaseous melt replenishment system

The operation of a silicon production technique was demonstrated. The essentials of the method comprise chemical vapor deposition of silicon, by hydrogen reduction of chlorosilanes, on the inside of a quartz reaction vessel having large internal surface area. The system was designed to allow successive deposition-melting cycles, with silicon removal being accomplished by discharging the molten silicon. The liquid product would be suitable for transfer to a crystal growth process, casting into solid form, or production of shots. A scaled-down prototype reactor demonstrated single pass conversion efficiency of 20 percent and deposition rates and energy consumption better than conventional Siemens reactors, via deposition rates of 365 microns/hr. and electrical consumption of 35 Kwhr/kg of silicon produced.

Jewett, D. N.↗

Correlation of Amine Swingbed On-Orbit CO2 Performance with a Hardware Independent Predictive Model

The Amine Swingbed Payload is an experimental system deployed on the International Space Station (ISS) that includes a two-bed, vacuum regenerated, amine-based carbon dioxide (CO2) removal subsystem as the principal item under investigation. The aminebased subsystem, also described previously in various publications as CAMRAS 3, was originally designed, fabricated and tested by Hamilton Sundstrand Space Systems International, Inc. (HSSSI) and delivered to NASA in November 2008. The CAMRAS 3 unit was subsequently designed into a flight payload experiment in 2010 and 2011, with flight test integration activities accomplished on-orbit between January 2012 and March 2013. Payload activation was accomplished in May 2013 followed by a 1000 hour experimental period. The experimental nature of the Payload and the interaction with the dynamic ISS environment present unique scientific and engineering challenges, in particular to the verification and validation of the expected Payload CO2 removal performance. A modeling and simulation approach that incorporates principles of chemical reaction engineering has been developed for the amine-based system to predict the dynamic cabin CO2 partial pressure with given inputs of sorbent bed size, process air flow, operating temperature, half-cycle time, CO2 generation rate, cabin volume and the magnitude of vacuum available. Simulation runs using the model to predict ambient CO2 concentrations show good correlation to on-orbit performance measurements and ISS dynamic concentrations for the assumed operating conditions. The dynamic predictive modelling could benefit operational planning to help ensure ISS CO2 concentrations are maintained below prescribed limits and for the Orion vehicle to simulate various operating conditions, scenarios and transients.

Papale, William↗