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13 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

Interstellar Grain Surface Chemistry

Chemistry on grain surfaces plays an Important role in the formation of interstellar Ices, It can also influence the composition of the gas phase through outgassing near luminous, newly formed stars. This paper reviews the chemical processes taking place on Interstellar grain surfaces with the emphasis on those transforming CO into other hydrocarbons. At low, molecular cloud temperatures (approximately equal to 10K), physisorption processes dominate interstellar grain surface chemistry and GO is largely hydrogenated through reactions with atomic H and oxidized through reactions with atomic O. The former will lead to the formation of H2CO and CH3OH ices, while the latter results in CO2 ice. The observational evidence for these ices in molecular clouds will be discussed. Very close to protostars, the gas and grain temperatures are much higher (approximately equal to 500K) and chemisorption processes, including catalytic surface reactions, becomes important. This will be illustrated based upon our studies of the Fischer-Tropsch Synthesis of CH4 from CO on metallic surfaces. Likely, this process has played an important role in the early solar nebula. Observational consequences will be pointed out.

Tielens, Alexander G. G. M.↗
NASA NTRS1990

Chemisorption studies of Pt/SnO2 catalysts

The low temperature CO oxidation catalysts that are being developed and tested at NASA-Langley are fairly unique in their ability to efficiently oxidize CO at low temperatures (approx. 303 K). The bulk of the reaction data that has been collected in the laboratory has been determined using plug flow reactors with a low mass of Pt/SnO2/SiO2 catalyst (approx. 0.1 g) and a modest flow rate (5 to 10 sc sm). The researchers have previously characterized the surface solely in terms of N2 BET surface areas. These surface areas have not been that indicative of reaction rate. Indeed, some of the formulations with high BET surface area have yielded lower reaction rates than those with lower BET surface areas. As a result researchers began a program of determining the chemisorption of the various species involved in the reaction; CO, O2 and CO2. Such a determination of will lead to a better understanding of the mechanism and overall kinetics of the reaction. The pulsed-reactor technique, initially described by Freel, is used to determine the amount of a particular molecule that is adsorbed on the catalyst. Since there is some reaction of CO with the surface to produce CO2, the pulsed reactor had to be coupled with a gas chromatograph in order to distinguish between the loss of CO that is due to adsorption by the surface and the loss that is due to reaction with the surface.

Brown, Kenneth G.↗
NASA NTRS1992

Spectral identification of chemisorbed CO2 and application to Mars analog materials

The goal of this work is to identify the spectral signature of chemisorbed CO2, to test the efficacy of carbonate formation on Mars-analog materials via CO2 chemisorption, and to identify the surface-chemical characteristics of good chemisorbents, with the intent of assessing the possible geochemical importance of CO2 chemisorption as a quasipermanent CO2 sink in the Martian environment. Our approach is to search for infrared spectral bands that result from chemisorption of CO2 molecules onto chemical reagents and Mars-analog materials, and to identify the salient differences in adsorbents that favor strong, permanent CO2 chemisorption. The total amount of CO2 in the early Martian atmosphere, and consequent surface temperatures, are unknown. A CO2 greenhouse may not have been an adequate mechanism under any circumstances; however, it if were, then most of that CO2 must still be in the near-surface environment; no escape mechanism that could remove it after the decline of channeling has been identified. The only plausible reservoir is carbonate, and there are various remote sensing techniques that can be used to search for it. We are investigating CO2 chemisorption as a permanent CO2 sink, and to aid in interpretation of remotely sensed IR spectra of Mars. A common effect reported in CO2 adsorption studies is the formation of a layer of carbonate or bicarbonate anions on adsorbents that have OH- groups available on their surfaces. Inorganic hydroxyls occur on phyllosilicates, amorphous silicates, metal oxides and hydroxides; it is the most abundant and reactive surface functional group on the surfaces of terrestrial silicates. The process responsible for the reaction is chemisorption. Chemisorption is distinguished from physical adsorption in that there is a transfer of electrons between species, and the formation of a chemical bond. The heat of chemisorption is typically of the same order as heats of chemical reaction (i.e., a few hundred to a few thousand kJ/mole), as opposed to heats of physical adsorption (a few kJ per mole). Chemisorption is an activated process that is promoted by an increase in temperature - quite the opposite of physical adsorption. Chemisorption is not reversible in the sense that physical adsorption is.

Zent, A. P.↗
NASA NTRS1981

Influence of hydrogen chemisorption kinetics on the interpretation of hydrogen transport through iron membranes

The influence of a specific surface reaction on the transport of gas-phase hydrogen through iron membranes has been investigated on the basis of model calculations. The surface reaction involves an adsorbed molecular hydrogen precursor between the gas phase and the dissociated chemisorbed state. The calculations demonstrate that the surface reaction for the H2/Fe system makes significant contributions to the time delay associated with the transient hydrogen transport through iron membranes, even under conditions where the steady-state hydrogen transport is independent of the surface reaction. These contributions to the time delay are interpreted in terms of an effective diffusivity, which is a function of the pressure on the entrance side and the thickness of the membrane.

Shanabarger, M. R.↗
NASA NTRS1976

The interaction of small particles and thin films of metals with gases. I - A brief review of the early stages of oxide formation

Existing work on gas-solid reactions making use of thin film technologies is reviewed. The discussion concentrates on two major areas of gas-metal interactions: chemisorption and the early stages of oxidation of metals (characterized by a non-volatile reaction product) and catalytic surface reactions (featuring volatile reaction products). A brief survey of oxide formation on metals is presented. Here it is of importance to distinguish between reactions on continuous thin film substrates and reactions on particulate deposits. Small particle-gas interactions also affect the nucleation, growth and sintering processes of thin films. It is shown that various combinations of UHV and high resolution electron microscopy techniques, which include in situ experimentation, can provide the appropriate tools for studying angstrom particle chemistry.

Poppa, H.↗
NASA NTRS1992

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Napier, Mary E.↗
NASA NTRS1990

In situ analysis of CO during chemisorption and oxidation on graphite: Supported Pt by FTIR-microspectrometry

For chemisorption and oxidation on Pt/HOPG (highly-orientated pyrolytic) graphite, reflectance Fourier Transform Infrared (FTIR)-microspectrometry reveals a variable state and reactivity for CO. Even for model surface science systems, where surface heterogeneity is minimal, surface diffusion may be too slow relative to the reaction rate to avoid segregation of reactants into surface islands under steady-state conditions. Thus in CO oxidation on Pt (where the relevant surface diffusion coefficients are such that D sub O less than D sub CO) then reactant CO islands exists at the perimeters of which the surface reaction is thought to occur. Furthermore CO can chemisorb on metals in linear and bridge forms to extents which vary with precise faces predominantly exposed coverage, etc. Infrared has long been used to probe the nature of adsorbed CO on model film and heterogeneous surfaces, but it may now be that FTIR-microspectrometry will allow the state of this adsorbate and reactant to be investigated with a spatial resolution of 4.4 microns on model (and real) catalytic surfaces.

Self, Valerie A.↗
NASA NTRS2003

Vacancy Mediated Mechanism of Nitrogen Substitution in Carbon Nanotubes

Nitrogen substitution reaction in a graphene sheet and carbon nanotubes of different diameter are investigated using the generalized tight-binding molecular dynamics method. The formation of a vacancy in curved graphene sheet or a carbon nanotube is found to cause a curvature dependent local reconstruction of the surface. Our simulations and analysis show that vacancy mediated N substitution (rather than N chemisorption) is favored on the surface of nanotubes with diameter larger than 8 nm. This predicted value of the critical minimum diameter for N incorporation is confirmed by experimental results presented.

Srivastava, Deepak↗
NASA NTRS1978

Adsorption and chemical reaction of gaseous mixtures of hydrogen chloride and water on aluminum oxide and application to solid-propellant rocket exhaust clouds

Hydrogen chloride (HCl) and aluminum oxide (Al2O3) are major exhaust products of solid rocket motors (SRM). Samples of calcination-produced alumina were exposed to continuously flowing mixtures of gaseous HCl/H2O in nitrogen. Transient sorption rates, as well as maximum sorptive capacities, were found to be largely controlled by specific surface area for samples of alpha, theta, and gamma alumina. Sorption rates for small samples were characterized linearly with an empirical relationship that accounted for specific area and logarithmic time. Chemisorption occurred on all aluminas studied and appeared to form from the sorption of about a 2/5 HCl-to-H2O mole ratio. The chemisorbed phase was predominantly water soluble, yielding chloride/aluminum III ion mole ratios of about 3.3/1 suggestive of dissolved surface chlorides and/or oxychlorides. Isopiestic experiments in hydrochloric acid indicated that dissolution of alumina led to an increase in water-vapor pressure. Dissolution in aqueous SRM acid aerosol droplets, therefore, might be expected to promote evaporation.

Cofer, W. R., III↗
NASA NTRS1980

An investigation of the kinetics for hydrogen chemisorption on iron metal surfaces

A quasi-isothermal approach was used to study the kinetics of hydrogen and hydrogen sulfide chemisorption onto iron film in an effort to understand the environmental degradation of steels. The coverage of chemisorbed hydrogen or chemisorbed sulfur was observed as a function of time for fixed conditions of substrate temperature. Auger electron spectroscopy was used to observe the sulfur and chemisorption-induced resistance change was employed to monitor hydrogen coverage. To compare the results obtained from studying the kinetics by two different techniques, the kinetics of oxygen chemisorption onto iron films was also studied. A reaction model utilized to interpret the H2/Fe2 chemisorption kinetics was applied to data from an earlier study on the desorption kinetics for H2 chemisorbed onto nicket films in the vicinity of the Curie temperature of the film. This analysis permitted a separation of the gross desorption process into individual components so that the influence of the magnetic phase transition on the rate constants could be determined.

Shanabarger, M. R.↗
NASA NTRS2000

Numerical Simulation of a Chemically Reacting Sorbent Bed for LSS Applications

A detailed numerical model of a chemisorption bed has been developed. The model is based on the constant pressure mass transport equation for gaseous flow through a packed bed, and the equation for diffusion and reaction within a spherical particle. Because there is a wealth of data from the NASA and the Navy bodies of literature, the LiOH-H2O-CO2 system is chosen for application of the model and interpretation of results. Prior models of this system from the life support literature are limited. The current model incorporates many of the features of elaborate models developed for investigation of industrial systems or energy applications (e.g., coal, desulphurization): it distinguishes bulk convection and bed dispersion; mass transport to the particle surface, transport within the particle, and reaction. It uses the nonsteady (not pseudo-steady state) form of the equations. The chemistry is modeled as a multi-step, reversible reaction with evolving solid structure. The resulting system of equations is large. The ODEPACK family of solvers is used to integrate the system. Reaction coefficients are determined by experiment. Typical results of the model are illustrated with mission input parameters. Using the model, an explanation is offered for 1) the varied performance results found after pre-breathing (or after simulated pre-breathe conditions), 2) interrupted use and 3) low temperature use. In addition, options for a reusable canister are explored. The computational resource implications of adding energy equations are discussed briefly, as are applicability to other relevant space and undersea systems.

Luna, Bernadette↗
NASA NTRS1992

Materials surface contamination analysis

The original research objective was to demonstrate the ability of optical fiber spectrometry to determine contamination levels on solid rocket motor cases in order to identify surface conditions which may result in poor bonds during production. The capability of using the spectral features to identify contaminants with other sensors which might only indicate a potential contamination level provides a real enhancement to current inspection systems such as Optical Stimulated Electron Emission (OSEE). The optical fiber probe can easily fit into the same scanning fixtures as the OSEE. The initial data obtained using the Guided Wave Model 260 spectrophotometer was primarily focused on determining spectra of potential contaminants such as HD2 grease, silicones, etc. However, once we began taking data and applying multivariate analysis techniques, using a program that can handle very large data sets, i.e., Unscrambler 2, it became apparent that the techniques also might provide a nice scientific tool for determining oxidation and chemisorption rates under controlled conditions. As the ultimate power of the technique became recognized, considering that the chemical system which was most frequently studied in this work is water + D6AC steel, we became very interested in trying the spectroscopic techniques to solve a broad range of problems. The complexity of the observed spectra for the D6AC + water system is due to overlaps between the water peaks, the resulting chemisorbed species, and products of reaction which also contain OH stretching bands. Unscrambling these spectral features, without knowledge of the specific species involved, has proven to be a formidable task.

Workman, Gary L.↗