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At least 397 records · Page 22

Pyrite oxidation and reduction - Molecular orbital theory considerations

In this paper, molecular orbital theory is used to explain a heterogeneous reaction mechanism for both pyrite oxidation and reduction. The mechanism demonstrates that the oxidation of FeS2 by Fe(3+) may occur as a result of three important criteria: (1) the presence of a suitable oxidant having a vacant orbital (in case of liquid phase) or site (solid phase) to bind to the FeS2 via sulfur; (2) the initial formation of a persulfido (disulfide) bridge between FeS2 and the oxidant, and (3) an electron transfer from a pi(asterisk) orbital in S2(2-) to a pi or pi(asterisk) orbital of the oxidant.

Luther, George W., III↗

Formation and Destruction Processes of Interstellar Dust: From Organic Molecules to carbonaceous Grains

The study of the formation and destruction processes of cosmic dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. interstellar dust presents a continuous size distribution from large molecules, radicals and ions to nanometer-sized particles to micron-sized grains. The lower end of the dust size distribution is thought to be responsible for the ubiquitous spectral features that are seen in emission in the IR (UIBs) and in absorption in the visible (DIBs). The higher end of the dust-size distribution is thought to be responsible for the continuum emission plateau that is seen in the IR and for the strong absorption seen in the interstellar UV extinction curve. All these spectral signatures are characteristic of cosmic organic materials that are ubiquitous and present in various forms from gas-phase molecules to solid-state grains. Although dust with all its components plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of dust. Recent space observations in the UV (HST) and in the IR (ISO) help place size constraints on the molecular component of carbonaceous IS dust and indicate that small (ie., subnanometer) PAHs cannot contribute significantly to the IS features in the UV and in the IR. Studies of large molecular and nano-sized IS dust analogs formed from PAH precursors have been performed in our laboratory under conditions that simulate diffuse ISM environments (the particles are cold -100 K vibrational energy, isolated in the gas phase and exposed to a high-energy discharge environment in a cold plasma). The species (molecules, molecular fragments, ions, nanoparticles, etc) formed in the pulsed discharge nozzle (PDN) plasma source are detected with a high-sensitivity cavity ring-down spectrometer (CRDS). We will present new experimental results that indicate that nanoparticles are generated in the plasma. From these unique measurements, we derive information on the nature, the size and the structure of interstellar dust particles, the growth and the destruction processes of IS dust and the resulting budget of extraterrestrial organic molecules.

Salama, F.↗

CuInS2 Films Deposited by Aerosol-Assisted Chemical Vapor Deposition Using Ternary Single-Source Precursors

Polycrystalline CuInS2 films were deposited by aerosol-assisted chemical vapor deposition using both solid and liquid ternary single-source precursors (SSPs) which were prepared in-house. Films with either (112) or (204/220) preferred orientation, had a chalcopyrite structure, and (112)-oriented films contained more copper than (204/220)-oriented films. The preferred orientation of the film is likely related to the decomposition and reaction kinetics associated with the molecular structure of the precursors at the substrate. Interestingly, the (204/220)-oriented films were always In-rich and were accompanied by a secondary phase. From the results of post-growth annealing, etching experiments, and Raman spectroscopic data, the secondary phase was identified as an In-rich compound. On the contrary, (112)-oriented films were always obtained with a minimal amount of the secondary phase, and had a maximum grain size of about 0.5 micron. Electrical and optical properties of all the films grown were characterized. They all showed p-type conduction with an electrical resistivity between 0.1 and 30 Omega-cm, and an optical band gap of approximately 1.46 eV +/- 0.02, as deposited. The material properties of deposited films revealed this methodology of using SSPs for fabricating chalcopyrite-based solar cells to be highly promising.

Jin, Michael↗

Moderate spectral resolution observations of 3 micron absorption features in highly obscured objects

The 3 micron absorption spectra of sources seen in or behind molecular clouds generally show a variety of absorption features. Three separate absorptions are used to explain these features. The cooled-grating array spectrometer (CGAS) at the NASA Infrared Telescope Facility was used to obtain spectra of the late-type mass-loss star OH 0739-12 and the protostars MonR2 IRS-2 and IRS-3 (solid circles). The differences between the spectra are discussed.

Smith, R. G.↗

Chemical investigation of Titan and Triton tholins

We report chromatographic and spectroscopic analyses of both Titan and Triton tholins, organic solids made from the plasma irradiation of 0.9:0.1 and 0.999:0.001 N2/CH4 gas mixtures, respectively. The lower CH4 mixing ratio leads to a nitrogen-richer tholin (N/C greater than 1), probably including nitrogen heterocyclic compounds. Unlike Titan tholin, bulk Triton tholin is poor in nitriles. From high-pressure liquid chromatography, ultraviolet and infrared spectroscopy, and molecular weight estimation by gel filtration chromatography, we conclude that (1) several H2O-soluble fractions, each with distinct UV and IR spectral signatures, are present, (2) these fractions are not identical in the two tholins, (3) the H2O-soluble fractions of Titan tholins do not contain significant amounts of nitriles, despite the major role of nitriles in bulk Titan tholin, and (4) the H2O-soluble fractions of both tholins are mainly molcules containing about 10 to 50 (C + N) atoms. We report yields of amino acids upon hydrolysis of Titan and Triton tholins. Titan tholin is largely insoluble in the putative hydrocarbon lakes or oceans on Titan, but can yield the H2O-soluble species investigated here upon contact with transient (e.g., impact-generated) liquid water.

Mcdonald, Gene D.↗

Comments on the origins of the diffuse interstellar bands

Most work in recent years on the unidentified diffuse interstellar bands has been concentrated on the hypothesis that they are produced by some process in solid grains. We review that hypothesis and the arguments which support it, and find that diffuse band formation by certain classes of molecules should not yet be ruled out. Since several relevant observations have been made in the last four years, the observational data on the bands are reviewed. It would appear that these data are as consistent with molecular origins for the bands as with grain origins. Types of molecular transitions which give rise to 'diffuse' bands are described. These transitions can occur in relatively simple molecules composed of cosmically abundant elements and can produce broad, unresolvable profiles without destroying the molecule. New observations are suggested which could produce decisive evidence with which to determine whether the diffuse bands originate in grains, molecules, or both.

Smith, W. H.↗

The determination of energy transfer rates in the Ho:Tm:Cr:YAG laser material

Energy transfer processes occurring between atomic, ionic, or molecular systems are very widespread in nature. The applications of such processes range form radiation physics and chemistry to biology. In the field of laser physics, energy transfer processes have been used to extend the lasing range, increase the output efficiency, and influence the spectral and temporal characteristics of the output pulses of energy transfer dye lasers or solid-state laser materials. Thus in the development of solid state lasers, it is important to investigate the basic energy transfer (ET) mechanisms and processes in order to gain detailed knowledge so that successful technical utilization can be achieved. The aim of the present research is to measure the ET rate from a given manifold associated with the chromium sensitizer atom to a given manifold in the holmium activator atom via the thulium transfer atom, in the Ho:Cr:YAG laser material.

Koker, Edmond B.↗

High Resolution 4.7 Micron Keck/NIRSPEC Spectra of Protostars: Ices and Infalling Gas in the Disk of L1489 IRS - 1

We explore the infrared M band (4.7 micron) spectrum of the class I protostar L1489 IRS in the Taurus Molecular Cloud. This is the highest resolution wide coverage spectrum at this wavelength of a low mass protostar observed to date (R =25,000; (Delta)v =12 km s(exp -1). A large number of narrow absorption lines of gas phase (12)CO, (13)CO, and C(sup 18)O are detected, as well as a prominent band of solid (12)CO. The gas phase (12)CO lines have red shifted absorption wings (up to 100 km s(exp -1)), which likely originate from warm disk material falling toward the central object. Both the isotopes and the extent of the (12)CO line wings are successfully fitted with a contracting disk model of this evolutionary transitional object. This shows that the inward motions seen in millimeter wave emission lines continue to within approx. 0.1 AU from the star. The amount of high velocity infalling gas is however overestimated by this model, suggesting that only part of the disk is infalling, e.g. a hot surface layer or hot gas in magnetic field tubes. The colder parts of the disk are traced by the prominent CO ice band. The band profile results from CO in 'polar' ices (CO mixed with H2O), and CO in 'apolar' ices. At the high spectral resolution, the 'apolar' component is, for the first time, resolved into two distinct components, likely due to pure CO and CO mixed with CO2, O2 and/or N2. The ices have probably experienced thermal processing in the upper disk layer traced by our pencil absorption beam: much of the volatile 'apolar' ices has evaporated, the depletion factor of CO onto grains is remarkably low (approx. 7%), and the CO2 traced in the CO band profile was possibly formed energetically. This study shows that high spectral resolution 4.7 micron observations provide important and unique information on the dynamics and structure of protostellar disks and the origin and evolution of ices in these disks.

Boogert, A. C. A.↗

Convection of tin in a Bridgman system. I - Flow characterization by effective diffusivity measurements

An electrochemical titration method was used to investigate the dynamic states in a cylindrical layer of convecting tin. The liquid tin was contained in a cell, with curved boundaries made of quartz and flat boundaries made of a solid state electrolyte - yttria-stabilized zirconia (YSZ). The electrolyte acted as a window through which a trace amount of oxygen could be pumped in or out by the application of a constant voltage. The concentration at the YSZ interface was monitored by operating the electrochemical cell in the galvanic mode. Experimentally determined effective diffusivities of oxygen were compared with the molecular diffusivity. Dynamic states in the convective flow were thus inferred. Temperature measurements were simultaneously made in order to identify the onset of oscillations from a steady convective regime. The experiments were conducted for two different aspect ratios for various imposed temperature gradients and two different orientations with respect to gravity. Transcritical states were identified and comparison to two-dimensional numerical models were made.

Sears, B.↗

Space Shuttle solid rocket motor exposure monitoring

During the processing of the Space Shuttle Solid Rocket Booster (SRB), segments at the Kennedy Space Center, an odor was detected around the solid propellant. An Industrial Hygiene survey was conducted to determine the chemical identity of the SRB offgassing constituents. Air samples were collected inside a forward SRB segment and analyzed to determine chemical composition. Specific chemical analysis for suspected offgassing constituents of the propellant indicated ammonia to be present. A gas chromatograph mass spectroscopy (GC/MS) analysis of the air samples detected numerous high molecular weight hydrocarbons.

Brown, S. W.↗

Exploration of the Habitability of Mars with the SAM Suite Investigation on the 2009 Mars Science Laboratory

The 2009 Mars Science Laboratory (MSL) with a substantially larger payload capability that any other Mars rover, to date, is designed to quantitatively assess a local region on Mars as a potential habitat for present or past life. Its goals are (1) to assess past or present biological potential of a target environment, (2) to characterize geology and geochemistry at the MSL landing site, and (3) to investigate planetary processes that influence habitability. The Sample Analysis at Mars (SAM) Suite, in its final stages of integration and test, enables a sensitive search for organic molecules and chemical and isotopic analysis of martian volatiles. MSL contact and remote surface and subsurface survey Instruments establish context for these measurements and facilitate sample identification and selection. The SAM instruments are a gas chromatograph (GC), a mass spectrometer (MS), and a tunable laser spectrometer (TLS). These together with supporting sample manipulation and gas processing devices are designed to analyze either the atmospheric composition or gases extracted from solid phase samples such as rocks and fines. For example, one of the core SAM experiment sequences heats a small powdered sample of a Mars rock or soil from ambient to -1300 K in a controlled manner while continuously monitoring evolved gases. This is followed by GCMS analysis of released organics. The general chemical survey is complemented by a specific search for molecular classes that may be relevant to life including atmospheric methane and its carbon isotope with the TLS and biomarkers with the GCMS.

Mahaffy, P. R.↗

Terabit Wireless Communication Challenges

This presentation briefly discusses a research effort on Terabit Wireless communication systems for possible space applications. Recently, terahertz (THz) technology (300-3000 GHz frequency) has attracted a great deal of interest from academia and industry. This is due to a number of interesting features of THz waves, including the nearly unlimited bandwidths available, and the non-ionizing radiation nature which does not damage human tissues and DNA with minimum health threat. Also, as millimeter-wave communication systems mature, the focus of research is, naturally, moving to the THz range. Many scientists regard THz as the last great frontier of the electromagnetic spectrum, but finding new applications outside the traditional niches of radio astronomy, Earth and planetary remote sensing, and molecular spectroscopy particularly in biomedical imaging and wireless communications has been relatively slow. Radiologists find this area of study so attractive because t-rays are non-ionizing, which suggests no harm is done to tissue or DNA. They also offer the possibility of performing spectroscopic measurements over a very wide frequency range, and can even capture signatures from liquids and solids. According to Shannon theory, the broad bandwidth of the THz frequency bands can be used for terabit-per-second (Tb/s) wireless communication systems. This enables several new applications, such as cell phones with 360 degrees autostereoscopic displays, optic-fiber replacement, and wireless Tb/s file transferring. Although THz technology could satisfy the demand for an extremely high data rate, a number of technical challenges need to be overcome before its development. This presentation provides an overview the state-of-the- art in THz wireless communication and the technical challenges for an emerging application in Terabit wireless systems. The main issue for THz wave propagation is the high atmospheric attenuation, which is dominated by water vapor absorption in the THz frequency band. The technical challenges in design such a system and the techniques to overcome the challenges will be discussed in this presentation.

Hwu, Shian U.↗

A computer simulation of the afterburning processes occurring within solid rocket motor plumes in the troposphere

As part of a continuing study of the environmental effects of solid rocket motor (SRM) operations in the troposphere, a numerical model was used to simulate the afterburning processes occurring in solid rocket motor plumes and to predict the quantities of potentially harmful chemical species which are created. The calculations include the effects of finite-rate chemistry and turbulent mixing. It is found that the amount of NO produced is much less than the amount of HCl present in the plume, that chlorine will appear predominantly in the form of HCl although some molecular chlorine is present, and that combustion is complete as is evident from the predominance of carbon dioxide over carbon monoxide.

Gomberg, R. I.↗

A spectroscopic study of intermediates in the condensation of refractory smokes: Matrix isolation experiments SiO

The infrared and Raman spectra of N2 matrix isolated silicon oxides are investigated. The vibrational frequencies of SiO, Si2O2, and Si3O3 were identified and assigned on the basis of normal coordinate analyses. Heating the solid to 50 K (evaporating the matrix) leaves a residue whose infrared spectrum is identical to that of a smoke condensed at ambient temperatures. Further heating of the sample to 500 K leads to significant changes in the band shapes. Investigations of the infrared spectra at several stages of the diffusion process result in the proposal of a mechanism for the transition from molecular properties to those of the residue (bulk) material, which is characterized as Si2O3.

Khanna, R. K.↗

In-Flight Water Quality Monitoring on the International Space Station (ISS): Measuring Biocide Concentrations with Colorimetric Solid Phase Extraction (CSPE)

The colorimetric water quality monitoring kit (CWQMK) was delivered to the International Space Station (ISS) on STS-128/17A and was initially deployed in September 2009. The kit was flown as a station development test objective (SDTO) experiment to evaluate the acceptability of colorimetric solid phase extraction (CSPE) technology for routine water quality monitoring on the ISS. During the SDTO experiment, water samples from the U.S. water processor assembly (WPA), the U.S. potable water dispenser (PWD), and the Russian system for dispensing ground-supplied water (SVO-ZV) were collected and analyzed with the CWQMK. Samples from the U.S. segment of the ISS were analyzed for molecular iodine, which is the biocide added to water in the WPA. Samples from the SVOZV system were analyzed for ionic silver, the biocide used on the Russian segment of the ISS. In all, thirteen in-flight analysis sessions were completed as part of the SDTO experiment. This paper provides an overview of the experiment and reports the results obtained with the CWQMK. The forward plan for certifying the CWQMK as operational hardware and expanding the capabilities of the kit are also discussed.

Gazda, Daniel B.↗

Compositions of the Surfaces of Pluto and its Satellites

The information we have on the chemical compositions of the surfaces of Pluto and Charon has been obtained from Earth-based near-infrared spectroscopy. These bodies are seen in diffusely scattered sunlight upon which absorption bands diagnostic of specific ices are superimposed. Identified so far on Pluto are molecular nitrogen (N2), methane (CH4), carbon monoxide (CO), and ethane (C2H6), all in the frozen state. Charon has the clear spectral signature of H2O ice in the crystalline phase, plus an absorption band near 2.2 microns identified as a hydrated form of NH3. No diagnostic spectra of Pluto's other satellites are currently available. A fraction of Pluto's CH4 is dissolved in solid N2, which is in the hexagonal beta-phase. When a small concentration of CH4 exists in a N2 crystalline matrix, its absorption bands are shifted in wavelength by a small but detectable amount. Indeed the shifting of the CH4 bands is diagnostic of a host matrix. In the case of Pluto, the N2 band (2.148 microns) itself is detected, but for other trans-Neptunian objects where the N2 band cannot be seen, the shifted CH4 bands demonstrate the presence of N2 or (less likely) some other spectrally neutral and transparent matrix material (e.g., Ar). The absence of detectable CO2 and H2O ices on Pluto, while they are clearly present on the otherwise very similar Triton, is noteworthy. The ices of Pluto distributed non-uniformly across its surface, and the distribution shows long-term (decadal) changes. Both seasonal and secular changes may be occurring through transport across the surface as a result of changing temperature, and by seasonal changes in the vapor pressure equilibrium of the ice with the tenuous and variable atmosphere. Models of the photochemistry of the surface ices and the atmosphere of Pluto predict the presence of several materials not yet detected; the most abundant photoproducts are expected to be C2H2, C4H2, HCN, C2H6; HCN has been detected on Triton. Both Pluto and Charon have surface components in addition to the detected ices. These materials of presently unknown composition serve to reduce the albedos of both bodies below that expected for pure ices, and in the case of Pluto impart a yellow-brown coloration; the color of Charon is more nearly neutral. It is generally thought that the non-ice components are more refractory than the ices and that they may be complex carbonaceous materials derived from the ultraviolet and charged particle processing of the surface ices. Minerals are also plausible candidates for the non-ice fraction. The refractory colored components may constitute bedrock upon which variable amounts of the ices are alternately deposited and evaporated as the seasons change. Water ice is expected to be a component of the bedrock, although it has not yet been reliably identified.

Pluto↗

A spectroscopic study of intermediates in the condensation of refractory smokes - Matrix isolation experiments of SiO

The infrared and Raman spectra of N2 matrix-isolated silicon oxides were investigated. The vibrational frequencies of SiO, Si2O2, and Si3O3 were identified and assigned on the basis of normal coordinate analyses. Heating the solid to approximately 50 K (evaporating the matrix) leaves a residue whose infrared spectrum is identical to that of a smoke condensed at ambient temperatures. Further heating of the sample to approximately 500 K leads to significant changes in the band shapes. Investigations of the infrared spectra at several stages of the diffusion process enable a mechanism to be proposed for the transition from molecular properties to those of the residue (bulk) material, which has been characterized as Si2O3.

Khanna, R. K.↗

Characterization and degradation studies on synthetic polymers for aerospace application

The anti-misting additive for jet fuels known as FM-9 (proprietary polymer) was characterized by elemental analysis, solubility studies and molecular weight determination. Physical properties of surface tension, viscosity, specific gravity and other physical parameters were determined. These results are compared with properties of polyisobutylene and fuels modified with the same; the misting characteristics of polyisobutylene and FM-9 in Jet A fuel are included. Characterization and degradation of phthalocyanine and its derivatives were accomplished by use of a mass spectrometer and a pyroprobe solid pyrolyzer. Metal phthalocyanine tetracarboxylic acids and phthalocyanine-tetraamine cured epoxies were studied. Epoxy/graphite composite panels were exposed to a NASA-Ames radiant panel fire simulator in the flaming and non-flaming modes; toxic gases of HCN and HZS were measured along with oxygen, Co2, Co, and organic gases.

Hsu, M. T. S.↗