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At least 163 records · Page 9

High-pressure metallization of FeO and implications for the earth's core

The phase diagram of FeO has been experimentally determined to pressures of 155 GPa and temperatures of 4000 K using shock-wave and diamond-cell techniques. A metallic phase of FeO is observed at pressures greater than 70 GPa and temperatures exceeding 1000 K. The metallization of FeO at high pressures implies that oxygen can be present as the light alloying element of the earth's outer core, in accord with the geochemical predictions of Ringwood (1977 and 1979). The high pressures necessary for this metallization suggest that the core has acquired its composition well after the initial stages of the earth's accretion. Direct experimental observations at elevated pressures and temperatures indicate that core-forming alloy can react chemically with oxides such as those forming the mantle. The core and mantle may never have reached complete chemical equilibrium, however. If this is the case, the core-mantle boundary is likely to be a zone of active chemical reactions.

Knittle, Elise↗

Study and modeling of finite rate chemistry effects in turbulent non-premixed flames

The development of numerical models that reflect some of the most important features of turbulent reacting flows requires information about the behavior of key quantities in well defined combustion regimes. In turbulent flames, the coupling between turbulent and chemical processes is so strong that it is extremely difficult to isolate the role played by one individual physical phenomenon. Direct numerical simulation (hereafter DNS) allows us to study in detail the turbulence-chemistry interaction in some restricted but completely defined situations. Globally, non-premixed flames are controlled by two limiting regimes: the fast chemistry case, where the turbulent flame can be pictured as a random distribution of local chemical equilibrium problems; and the slow chemistry case, where the chemistry integrates in time the turbulent fluctuations. The Damkoehler number, ratio of a mechanical time scale to chemical time scale, is used to distinguish between these regimes. Today most of the industrial computer codes are able to perform predictions in the hypothesis of local equilibrium chemistry using a presumed shape for the probability density function (pdt) of the conserved scalar. However, the finite rate chemistry situation is of great interest because industrial burners usually generate regimes in which, at some points, the flame is undergoing local extinction or at least non-equilibrium situations. Moreover, this variety of situations strongly influences the production of pollutants. To quantify finite rate chemistry effect, the interaction between a non-premixed flame and a free decaying turbulence is studied using DNS. The attention is focused on the dynamic of extinction, and an attempt is made to quantify the effect of the reaction on the small scale mixing process. The unequal diffusivity effect is also addressed. Finally, a simple turbulent combustion model based on the DNS observations and tractable in real flow configurations is proposed.

Vervisch, Luc↗

Viscous equilibrium computations using program LAURA

Modifications have been made to the Langley Aerothermodynamic Upwind Relaxation Algorithm (LAURA) that enable it to compute viscous airflows under the assumption of thermal and chemical equilibrium. Equilibrium thermodynamic and transport property information are input to the code via curve fits. The periodic updating of this information enables the equilibrium algorithm to perform at a computational rate that is only a small percentage larger than the rate associated with the perfect-gas algorithm. Presented in this article are the results of the initial validation of the modified code. Solutions for surface pressure and heating are presented for the flow over slender and blunt cones at realistic reentry conditions. LAURA solutions are compared with those produced by a viscous shock-layer method, and, for one case considered, with heat transfer data from a flight experiment. For both pressure and heating, the agreement is good. In general, differences in pressure of a few percent were noted, while differences in heating rates were in the 5-10 percent range.

Greene, Francis A.↗

Finite-Difference Solution for Laminar or Turbulent Boundary Layer Flow over Axisymmetric Bodies with Ideal Gas, CF4, or Equilibrium Air Chemistry

A computer code was developed that uses an implicit finite-difference technique to solve nonsimilar, axisymmetric boundary layer equations for both laminar and turbulent flow. The code can treat ideal gases, air in chemical equilibrium, and carbon tetrafluoride (CF4), which is a useful gas for hypersonic blunt-body simulations. This is the only known boundary layer code that can treat CF4. Comparisons with experimental data have demonstrated that accurate solutions are obtained. The method should prove useful as an analysis tool for comparing calculations with wind tunnel experiments and for making calculations about flight vehicles where equilibrium air chemistry assumptions are valid.

Hamilton, H. Harris, II↗

Catalytic recombination of nitrogen and oxygen on high-temperature reusable surface insulation

The energy transfer catalytic recombination coefficient for nitrogen and oxygen recombination on the surface coating of high-temperature reusable surface insulation (HRSI) is inferred from stagnation point heat flux measurements in a high-temperature dissociated arc jet flow. The resulting catalytic recombination coefficients are correlated with an Arrhenius model for convenience, and these expressions may be used to account for catalytic recombination effects in predictions of the heat flux on the HRSI thermal protection system of the Space Shuttle Orbiter during reentry flight. Analysis of stagnation point pressure and total heat balance enthalpy measurements indicates that the arc heater reservoir conditions are not in chemical equilibrium. This is contrary to what is usually assumed for arc jet analysis and indicates the need for suitable diagnostics and analyses, especially when dealing with chemical reaction phenomena such as catalytic recombination heat transfer effects.

Scott, C. D.↗

High speed turbulent reacting flows: DNS and LES

Work on understanding the mechanisms of mixing and reaction in high speed turbulent reacting flows was continued. Efforts, in particular, were concentrated on taking advantage of modern computational methods to simulate high speed turbulent flows. In doing so, two methodologies were used: large eddy simulations (LES) and direct numerical simulations (DNS). In the work related with LES the objective is to study the behavior of the probability density functions (pdfs) of scalar properties within the subgrid in reacting turbulent flows. The data base obtained by DNS for a detailed study of the pdf characteristics within the subgrid was used. Simulations are performed for flows under various initializations to include the effects of compressibility on mixing and chemical reactions. In the work related with DNS, a two-dimensional temporally developing high speed mixing layer under the influence of a second-order non-equilibrium chemical reaction of the type A + B yields products + heat was considered. Simulations were performed with different magnitudes of the convective Mach numbers and with different chemical kinetic parameters for the purpose of examining the isolated effects of the compressibility and the heat released by the chemical reactions on the structure of the layer. A full compressible code was developed and utilized, so that the coupling between mixing and chemical reactions is captured in a realistic manner.

Givi, Peyman↗

Influence of nonequilibrium radiation and shape change on aerothermal environment of a Jovian entry body

The influence of nonequilibrium radiative energy transfer and the effect of probe configuration changes on the flow phenomena around a Jovian entry body are investigated. The radiating shock layer flow is assumed to be axisymmetric, viscous, laminar and in chemical equilibrium. The radiative transfer equations are derived under nonequilibrium conditions which include multilevel energy transitions. The equilibrium radiative transfer analysis is performed with an existing nongray radiation model which accounts for molecular band, atomic line, and continuum transitions. The nonequilibrium results are obtained with and without ablation injection in the shock layer. The nonequilibrium results are found to be greatly influenced by the temperature distribution in the shock layer. In the absence of ablative products, the convective and radiative heating to the entry body are reduced under nonequilibrium conditions. The influence of nonequilibrium is found to be greater at higher entry altitudes. With coupled ablation and carbon phenolic injection, 16 chemical species are used in the ablation layer for radiation absorption. Equilibrium and nonequilibrium results are compared under peak heating conditions.

Tiwari, S. N.↗

Modeling Chemical and Isotopic Variations in Lab Formed Hydrothermal Carbonates

Chemical and mineralogical data (e.g. [1]) from Mars suggest that the history of liquid water on the planet was more sporadic in nature than long-lived. The non-equilibrium chemical and isotopic compositions of the carbonates preserved in the martian meteorite ALH84001 are direct evidence of ancient secondary minerals that have not undergone significant diagenesis or stabilization processes typical of long-lived aqueous systems on Earth. Thus secondary minerals and sediments on Mars may primarily record the characteristics of the aqueous environment in which they formed without being significantly overprinted by subsequent diagenetic processes during burial.

Niles, P. B.↗

Review and analysis of high temperature chemical reactions and the effect of non-equilibrium conditions

Chemical reactions at high temperatures have been considered extensively because of their importance to the heating effects on re-entry of space vehicles. Data on these reactions however, are not abundant and even when found there are discrepancies in data collected by various investigators. In particular, data for recombination reactions are calculated from the dissociation reactions or vice versa through the equilibrium constant. This involves the use of the principle of detailed balancing. This principle is discussed in reference to conditions where it is valid as well as to those where it is not valid. Related topics that merit further study or for which applicable information was available are briefly mentioned in an appendix to this report.

Johnson, R. E.↗

Detection of Extraterrestrial Ecology (Exoecology)

Researchers in the Astrobiology Technology Branch at Ames Research Center have begun investigating alternate concepts for the detection of extraterrestrial life. We suggest searching for extraterrestrial ecology, exoecology, as well as for extraterrestrial biology, exobiology. Ecology describes the interactions of living things with their environment. All ecosystems are highly constrained by their environment and are constrained by well-known system design principles. Ecology could exist wherever there is an energy source and living I things have discovered some means to capture, store, and use the available energy. Terrestrial ecosystems use as energy sources, light, organic molecules, and in thermal vents and elsewhere, simple inorganic molecules. Ecosystem behavior is controlled by matter and energy conservation laws and can be described by linear and nonlinear dynamic systems theory. Typically in an ecosystem different molecules are not in chemical equilibrium and scarce material is conserved, stored, or recycled. Temporal cycles and spatial variations are often observed. These and other -eneral principles of exoecology can help guide the search for extraterrestrial life. The chemical structure observed in terrestrial biology may be highly contingent on evolutionary accidents. Oxygen was not always abundant on Earth. Primitive sulfur bacteria use hydrogen sulfide and sulfur to perform photosynthesis instead of water and oxygen. Astrobiologists have assumed, for the sake of narrowing and focusing our life detection strategies, that extraterrestrial life will have detailed chemical similarities with terrestrial life. Such assumptions appear very reasonable and they allow us to design specific and highly sensitive life detection experiments. But the fewer assumptions we make, the less chance we have of being entirely wrong The best strategy for the detection of extraterrestrial life could be a mixed strategy. We should use detailed assumptions based on terrestrial biology to guide some but not all future searches for alien life. The systems principles of exoecology seem much more fundamental and inescapable than the terrestrial biology analogies of exobiology. We should search for exoecology as well as exobiology.

Jones, Harry↗

Influence of nonequilibrium radiation on heating of an ablating Jovian entry probe

The influence of non-local thermodynamic equilibrium (NLTE) radiative transfer on the entire shock-layer flow phenomena around a Jovian entry body is investigated. The flow in the shock layer is assumed to be viscous, axisymmetric, laminar, and in chemical equilibrium. The entry body considered is a 35-deg hyperboloid and the results have been obtained for the peak heating entry conditions. The results indicate that the radiative heating of the entry body is significantly higher under NLTE conditions.

Tiwari, S. N.↗

Volatile element chemistry in the solar nebula - Na, K, F, Cl, Br, and P

The results of the most extensive set to date of thermodynamic calculations on the equilibrium chemistry of several hundred compounds of the elements Na, K, F, Cl, Br, and P in a solar composition system are reported. Two extreme models of accretion are investigated. In one extreme complete chemical equilibrium between condensates and gases is maintained because the time scale for accretion is long compared to the time scale for cooling or dissipation of the nebula. Condensates formed in this homogeneous accretion model include several phases such as whitlockite, alkali feldspars, and apatite minerals which are found in chondrites. In the other extreme complete isolation of newly formed condensates from prior condensates and gases occurs due to a time scale for accretion that is short relative to the time required for nebular cooling or dissipation. The condensates produced in this heterogeneous accretion model include alkali sulfides, ammonium halides, and ammonium phosphates. None of these phases are found in chondrites. Available observations of the Na, K, F, Cl, Br, and P elemental abundances in the terrestrial planets are found to be compatible with the predictions of the homogeneous accretion model.

Fegley, B., Jr.↗

Cloud chemistry on Jupiter

Chemical equilibrium models used currently to interpret observations of Jupiter are reexamined using new data defining thermal profiles, which are substantially different from those used in the previous models. A model is developed for the chemical reactions controlling the composition of the upper troposphere on Jupiter, specifically the cloud-forming region from 10 bar to 0.1 bar, which includes, for the first time, the effects of aqueous chemistry on the composition and the vertical distribution of many measurable species in the atmosphere, identifying the factors influencing their abundances above the H2O cloud. The thermodynamic data for potential condensates on Jupiter, i.e., NH3(s), NH4SH(s), (NH4)2S(s), and H2S(s), are reexamined, recognizing the lack of data on sulfides for the temperature range of interest on Jupiter. Vertical profiles of mixing ratios for CO2, H2S, NH3, and H2, obtained for several assumed bulk abundances with respect to solar, are presented.

Carlson, Barbara E.↗

Real gas effects on hypersonic boundary-layer stability

High-temperature effects alter the physical and transport properties of a gas, air in particular, due to vibrational excitation and gas dissociation, and thus the chemical reactions have to be considered in order to compute the flow field. Linear stability of high-temperature boundary layers is investigated under the assumption of chemical equilibrium and this gas model is labeled here as real gas model. In this model, the system of stability equations remains of the same order as for the perfect gas and the effect of chemical reactions is introduced only through mean flow and gas property variations. Calculations are performed for Mach 10 and 15 boundary layers and the results indicate that real gas effects cause the first mode instability to stabilize while the second mode is made more unstable. It is also found that the second mode instability shifts to lower frequencies. There is a slight destabilizing influence of real gas on the Goertler instability as compared to the perfect gas results.

Malik, M. R.↗

Flux Jacobian Matrices For Equilibrium Real Gases

Improved formulation includes generalized Roe average and extension to three dimensions. Flux Jacobian matrices derived for use in numerical solutions of conservation-law differential equations of inviscid flows of ideal gases extended to real gases. Real-gas formulation of these matrices retains simplifying assumptions of thermodynamic and chemical equilibrium, but adds effects of vibrational excitation, dissociation, and ionization of gas molecules via general equation of state.

Vinokur, Marcel↗

The NATA code; theory and analysis. Volume 2: User's manual

The NATA code is a computer program for calculating quasi-one-dimensional gas flow in axisymmetric nozzles and rectangular channels, primarily to describe conditions in electric archeated wind tunnels. The program provides solutions based on frozen chemistry, chemical equilibrium, and nonequilibrium flow with finite reaction rates. The shear and heat flux on the nozzle wall are calculated and boundary layer displacement effects on the inviscid flow are taken into account. The program contains compiled-in thermochemical, chemical kinetic and transport cross section data for high-temperature air, CO2-N2-Ar mixtures, helium, and argon. It calculates stagnation conditions on axisymmetric or two-dimensional models and conditions on the flat surface of a blunt wedge. Included in the report are: definitions of the inputs and outputs; precoded data on gas models, reactions, thermodynamic and transport properties of species, and nozzle geometries; explanations of diagnostic outputs and code abort conditions; test problems; and a user's manual for an auxiliary program (NOZFIT) used to set up analytical curvefits to nozzle profiles.

Bade, W. L.↗

Coefficients for calculating thermodynamic and transport properties of individual species

Libraries of thermodynamic data and transport properties are given for individual species in the form of least-squares coefficients. Values of C(sup 0)(sub p)(T), H(sup 0)(T), and S(sup 0)(T) are available for 1130 solid, liquid, and gaseous species. Viscosity and thermal conductivity data are given for 155 gases. The original C(sup 0)(sub p)(T) values were fit to a fourth-order polynomial with integration constants for H(sup 0)(T) and S(sup 0)(T). For each species the integration constant for H(sup 0)(T) includes the heat of formation. Transport properties have a different functional form. The temperature range for most of the data is 300 to 5000 K, although some of the newer thermodynamic data have a range of 200 to 6000 K. Because the species are mainly possible products of reaction, the data are useful for chemical equilibrium and kinetics computer codes. Much of the data has been distributed for several years with the NASA Lewis equilibrium program CET89. The thermodynamic properties of the reference elements were updated along with about 175 species that involve the elements carbon, hydrogen, oxygen, and nitrogen. These sets of data will be distributed with the NASA Lewis personal computer program for calculating chemical equilibria, CETPC.

Mcbride, Bonnie J.↗

Earth's Early Biosphere and the Biogeochemical Carbon Cycle

Our biosphere has altered the global environment principally by influencing the chemistry of those elements most important for life, e g., C, N, S, O, P and transition metals (e.g., Fe and Mn). The coupling of oxygenic photosynthesis with the burial in sediments of photosynthetic organic matter, and with the escape of H2 to space, has increased the state of oxidation of the Oceans and atmosphere. It has also created highly reduced conditions within sedimentary rocks that have also extensively affected the geochemistry of several elements. The decline of volcanism during Earth's history reduced the flow of reduced chemical species that reacted with photosynthetically produced O2. The long-term net accumulation of photosynthetic O2 via biogeochemical processes has profoundly influenced our atmosphere and biosphere, as evidenced by the O2 levels required for algae, multicellular life and certain modem aerobic bacteria to exist. When our biosphere developed photosynthesis, it tapped into an energy resource that was much larger than the energy available from oxidation-reduction reactions associated with weathering and hydrothermal activity. Today, hydrothermal sources deliver globally (0.13-1.1)x10(exp l2) mol yr(sup -1) of reduced S, Fe(2+), Mn(2+), H2 and CH4; this is estimated to sustain at most about (0.2-2)xl0(exp 12)mol C yr(sup -1) of organic carbon production by chemautotrophic microorganisms. In contrast, global photosynthetic productivity is estimated to be 9000x10(exp 12) mol C yr(sup -1). Thus, even though global thermal fluxes were greater in the distant geologic past than today, the onset of oxygenic photosynthesis probably increased global organic productivity by some two or more orders of magnitude. This enormous productivity materialized principally because oxygenic photosynthesizers unleashed a virtually unlimited supply of reduced H that forever freed life from its sole dependence upon abiotic sources of reducing power such as hydrothermal emanations and weathering. Communities sustained by oxygenic photosynthesis apparently thrived wherever supplies of sunlight, moisture and nutrients were sufficient. Prior to the development of oxygenic photosynthesis, the net global effect of the ancient global biosphere was to facilitate chemical equilibrium between reduced species from thermal activity and weathering and more oxidized constituents in the surface environment. But even this ancient biosphere might have been globally pervasive. The global geothermal heat flow was substantially higher during Earth's first billion years, and thus reduced chemical species might have persisted in sunlit aquatic environments. Perhaps the substantial decline in thermal activity between 4000 and 3000 Ma created a driver for oxygenic photosynthesis to develop.

DesMarais, David↗