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At least 559 records · Page 31

High-resolution spectroscopy of H2SO4, HDSO4, and D2SO4 vapor in the region 1200-10,000 cm(-1)

The high-resolution (0.05 cm(-1)) spectra of gas-phase H2SO4, HDSO4, and D2SO4 were measured over the frequency region 1200-10,000 cm(-1) using Fourier-transform infrared spectroscopy. The increased resolution of this work compared with previous studies has lead to an improved vibrational analysis of H2SO4. This study has answered unresolved questions about combination bands and overlapping features from previous gas-phase spectroscopic studies of H2SO4 and marks the first experimental measurement of the nu8 and nu15 torsional vibrations in this molecule. This work leads to a brief discussion on vibrational mode mixing in sulfuric acid.

Deuterium/chemistry↗

Detection of [SiLL] (34.8 micron) emission in Orion-KL: A measurement of the silicon abundance in dense interstellar gas

The first detection of the ground state fine structure transition of Si+ at a rest wavelength determined to be 34.815 + or - 0.004 micron are reported. These observations were obtained with the facility spectrometer on NASA's Kuiper Airborne Observatory. A 6' NW-SE strip scan across the Orion-KL region shows SiII emission from both the extended photodissociation region surrounding theta 1 Ori C and from the shocked gas NW of BN-KL. The inferred gas-phase silicon elemental abundance relative to hydrogen in the dense 10 to the 5/cc primarily neutral photodissociation region is approximately 2.6 x to the -6, a factor of 0.075 times the solar value and 3.4 times greater than the abundance in the moderate density approx. 10 to the 3/cc cloud toward zeta Oph. The silicon abundance in the shocked gas is approximately solar, indicating that any pre-existing grains have been destroyed in the shock wave or that the preshock gas carries a near solar abundance of gas phase silicon. The shock-excited SiII (34.8 micron) emission may arise from shocked wind material in the outflow around IRc2, with wind velocities approx. 100 km/s.

Haas, M. R.↗

Detection of (Si II) (34.8 micron) emission in Orion-KL - A measurement of the silicon abundance in dense interstellar gas

The first detection of the ground state fine structure transition of Si+ at a rest wavelength determined to be 34.815 + or - 0.004 micron are reported. These observations were obtained with the facility spectrometer on NASA's Kuiper Airborne Observatory. A 6' NW-SE strip scan across the Orion-KL region shows Si II emission from both the extended photodissociation region surrounding theta 1 Ori C and from the shocked gas NW of BN-KL. The inferred gas-phase silicon elemental abundance relative to hydrogen in the dense 10 to the 5/cc primarily neutral photodissociation region is approximately 2.6 x 10 the -6, a factor of 0.075 times the solar value and 3.4 times greater than the abundance in the moderate density aprox. 10 to the 3/cc cloud toward Zeta Oph The silicon abundance in the shocked gas is approximately solar, indicating that any pre-existing grains have been destroyed in the shock wave or that the preshock gas carries a near solar abundance of gas phase silicon. The shock-excited Si II (34.8 micron) emission may arise from shocked wind material in the outflow around IRc2, with wind velocities approx. 100 km/s.

Haas, M. R.↗

Ignition delay of a gas mixture above a liquid fuel pool

A computational study has been made of transient heat transfer and fluid flow of an axisymmetric two-layer gas-and-liquid system heated from above by a small hot spot (e.g., a hot wire or pilot flame) located close to the liquid surface. The gas phase is unconfined above the liquid pool. The effects of varying gravity level (0.0001 to 1 gn), liquid pool height, and heater height are investigated. Thermocapillary convection induced by the nonuniform heating of the liquid surface combines with buoyancy forces to affect the heat transfer and the transport of fuel vapor toward the heat source. At reduced gravity, gas-phase conduction is comparable to the incident radiation at the liquid surface, whereas at 1 gn, buoyant convection carries the heat upward from the heat source and, therefore, the liquid is heated primarily by radiation.

Schiller, D. N.↗

Three-dimensional model interpretation of NO(x) measurements from the lower stratosphere

A three-dimensional off-line chemistry transport model, driven by European Center for Medium-Range Forecasts winds and temperatures, is used to interpret measurements of NO and NO2 taken from the DC-8 during the second Airborne Arctic Stratospheric Expedition. The model was run in three configurations: gas phase chemistry alone, inclusion of the N2O5 aerosol reaction, and inclusion of both N2O5 and ClONO2 aerosol reactions. The run including the N2O5 aerosol reaction alone usually agreed best with measured NO(x)/NO(y) ratios in midlatitude air masses. The NO(x)/NO(y) ratios of the run with both aerosol reactions were always too low, while the gas phase ratios were usually too high, especially during March. All three simulations generated extremely low NO2/NO(y) ratios in air parcels that had spent several days or more in the polar night. Measured NO2/NO(y) ratios in these types of air masses were sometimes equally low but could also be considerably higher. Observed NO/NO2 ratios differed strongly from known theory.

Folkins, Ian↗

Laminar Soot Processes (LSP) Experiment: Findings From Space Flight Measurements

The present experimental study of soot processes in hydrocarbon-fueled laminar nonbuoyant and nonpremixed (diffusion) flames at microgravity within a spacecraft was motivated by the relevance of soot to the performance of power and propulsion systems, to the hazards of unwanted fires, and to the emission of combustion-generated pollutants. Soot processes in turbulent flames are of greatest practical interest, however, direct study of turbulent flames is not tractable because the unsteadiness and distortion of turbulent flames limit available residence times and spatial resolution within regions where soot processes are important. Thus, laminar diffusion flames are generally used to provide more tractable model flame systems to study processes relevant to turbulent diffusion flames, justified by the known similarities of gas-phase processes in laminar and turbulent diffusion flames, based on the widely-accepted laminar flamelet concept of turbulent flames. Unfortunately, laminar diffusion flames at normal gravity are affected by buoyancy due to their relatively small flow velocities and, as discussed next, they do not have the same utility for simulating the soot processes as they do for simulating the gas phase processes of turbulent flames.

Sunderland, P. B.↗

Diffusion NMR methods applied to xenon gas for materials study

We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack. c2002 John Wiley & Sons, Ltd.

NASA Discipline Life Sciences Technologies↗

Accurate and reliable thermochemistry by data analysis of complex thermochemical networks using Active Thermochemical Tables: the case of glycine thermochemistry

Active Thermochemical Tables (ATcT) were successfully used to resolve the existing inconsistencies related to the thermochemistry of glycine, based on statistically analyzing and solving a thermochemical network that includes >3350 chemical species interconnected by nearly 35 000 thermochemically-relevant determinations from experiment and high-level theory. Here, the current ATcT results for the 298.15 K enthalpies of formation are −394.70 ± 0.55 kJ mol −1 for gas phase glycine, −528.37 ± 0.20 kJ mol −1 for solid α-glycine, −528.05 ± 0.22 kJ mol −1 for β-glycine, −528.64 ± 0.23 kJ mol −1 for γ-glycine, −514.22 ± 0.20 kJ mol −1 for aqueous undissociated glycine, and −470.09 ± 0.20 kJ mol −1 for fully dissociated aqueous glycine at infinite dilution. In addition, a new set of thermophysical properties of gas phase glycine was obtained from a fully corrected nonrigid rotor anharmonic oscillator (NRRAO) partition function, which includes all conformers. Corresponding sets of thermophysical properties of α-, β-, and γ-glycine are also presented.

Active Thermochemical Tables↗

Facile Generation of Active Sites in Nodes of Ni-MFU-4l Metal–Organic Framework for Hydrogenation Reaction

Metal–organic frameworks (MOFs) represent a well-defined class of materials capable of incorporating catalytically active sites for gas-phase catalysis. However, the reducing conditions of hydrogenation catalysis can lead to nanoparticle formation in MOFs, which can significantly diminish the catalytic activity of single-site metals and reduce the longevity of MOF-based hydrogen solutions. In this work, we present a straightforward approach to accessing catalytically active single metal sites in a robust Ni-MFU-4l MOF for gas-phase hydrogenation without the formation of Ni nanoparticles. By carefully tuning the local node chemistry through postsynthetic exchange of the terminal ligand coordinated to the Ni(II) centers in the MOF, from −Cl to −OH or −HCOO, we can readily generate Ni–H active species. We further demonstrate, using in situ pair-distribution function analysis, that these Ni–H sites are the sole catalytically active sites in the terminal ligand-exchanged counterparts, whereas nanoparticles readily form in the parent Ni-MFU-4l-Cl under otherwise identical catalytic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water vapor in the Orion Molecular Cloud

Infrared observations of interstellar gas-phase H2O in the spectrum of the BN object in Orion are reported. There are absorptions (S/N = 2-5) at the positions of four of the strong lines in the 000-001 nu3 vibration-rotation band. With an estimated excitation temperature of 150 K, the column density of gaseous H2O toward BN in the OMC-1 cloud is (2 + or - 1) x 10 to the 17th/sq cm. The intensities of the lines imply an ortho/para ratio of 1 + or - 0.5 indicating recent sublimation of H2O from low-temperature grains. The results give gas-phase abundance ratios of H2O/CO roughly 0.03 + or - 0.02 and HDO/H2O = 0.001-0.0001 toward BN. The velocities of the H2O absorptions agree with those of the ridge source and CO outflow, but the position along the line of sight is not well constrained. The gas/solid ratio is H2O(gas)/H20(ice) = 0.05 or less. Less than 1 percent of the oxygen is in H2O gas (assuming total cosmic abundance). Most of the H2O in the line of sight to BN, and by inference in quiescent regions of molecular clouds generally, is frozen on grains.

Knacke, R. F.↗

Mechanism for forming hydrogen chloride and sodium sulfate from sulfur trioxide, water, and sodium chloride

A molecular orbital study of sodium sulfate and hydrogen chloride formation from sulfur trioxide, water, and sodium chloride shows no activation barrier, in agreement with recent experimental work of Kohl, Fielder, and Stearns. Two overall steps are found for the process. First, gas-phase water reacts with sulfur trioxide along a pathway involving a linear O-H-O transition state yielding closely associated hydroxyl and bisulfite which rearrange to become a hydrogen sulfate molecule. Then the hydrogen sulfate molecule transfers a hydrogen atom to a surface chloride in solid sodium chloride while an electron and a sodium cation simultaneously transfer to yield sodium bisulfate and gas-phase hydrogen chloride. This process repeats. Both of these steps represent well-known reactions for which mechanisms have not been previously determined.

Anderson, A. B.↗

Energetic Processing of Interstellar Ices: A Route to Complexity

More than 140 gas-phase molecules have been detected in the interstellar (IS) medium or in circumstellar environments including inorganics, organics, ions, and radicals. The significant abundance of large, complex organic molecules, and families of isomers in these regions makes the origin and formation history of these species the subject of debate. Observationally determined condensed-phase species are H2O, CO, CO2, NH3 and CH30H, with CH4, HCOOH, OCS, OCN-, H2CO and NH4(+) present at trace levels. These ices can undergo energetic processing with cosmic rays or far-UV photons to form larger complex organics with abundance levels that make them undetectable in icy mantles. Once warmed, however, it is likely that these complex species would enter the gas-phase where they might be detected by Herschel or Alma. Understanding the role of radiation chemistry and thermal processing of ices and identifying new products are the goals of our laboratory research. In the Cosmic lee Laboratory at NASA Goddard Space Plight Center, we can study both the photo-and radiation chemistries of ices from 8 -- 300 K. Using dear- and mid-IR spectroscopy we can follow the destruction of primary molecules and the formation of radicals and secondary products as a function of energetic processing. During warming we can monitor the trapping of species and the results of any thermal chemistry. An overview of recent and past work will focus on complex secondary radiation products from small condensed-phase IS species. Likely reactions include dimerization, isomerization, H-addition and H-elimination. Another focus of our work is the development of reaction schemes for the formation of complex molecules and the use of such schemes to predict new molecules awaiting detection by Herschel and Alma.

Moore, Marla H.↗

Aircraft Particle Emissions eXperiment (APEX)

APEX systematically investigated the gas-phase and particle emissions from a CFM56-2C1 engine on NASA's DC-8 aircraft as functions of engine power, fuel composition, and exhaust plumage. Emissions parameters were measured at 11 engine power, settings, ranging from idle to maximum thrust, in samples collected at 1, 10, and 30 m downstream of the exhaust plane as the aircraft burned three fuels to stress relevant chemistry. Gas-phase emission indices measured at 1 m were in good agreement with the ICAO data and predictions provided by GEAE empirical modeling tools. Soot particles emitted by the engine exhibited a log-normal size distribution peaked between 15 and 40 nm, depending on engine power. Samples collected 30 m downstream of the engine exhaust plane exhibited a prominent nucleation mode.

Wey, C. C.↗

Laser diagnostics for microgravity droplet studies

An instrument has been designed, built, and tested for performing laser diagnostic measurements of droplet combustion in low-gravity-flight aircraft. Nonintrusive measurements are of particular importance for droplet combustion (the simplest example of non-premixed combustion) and transport in microgravity environments, where physical contact would introduce an unacceptable level of perturbations. The resolution of these diagnostics can also isolate transport to length scales much smaller than the droplet diameter. These techniques can be configured to instantaneously map an entire flow field in two and three dimensions, providing either qualitative or quantitative information on the distribution of a desired scalar or vector quantity. Detailing the gas-phase flow field and position of the flame front can be achieved using planar laser-induced fluorescence (PLIF) of OH or another flame front marker. An alternative approach is to obtain LIF from a diagnostic seed included in the liquid phase fuel; it would be consumed at the flame front. The main advantage to this approach is that it is easier to choose the wavelength of the molecular absorption which coincides with convenient laser wavelengths rather than finding lasers which can be configured to access OH. Our present method uses a nitrogen-pumped dye laser tuned to a sodium absorption and addition of small concentrations of NaCl to the fuel. Particle image velocimetry (PIV) is a laser-based technique which has recently had its practicality greatly enhanced by the development of high-resolution CCD cameras and the increase in speed and capacity of computer systems. With this technique, a seeded flow is illuminated with a double-pulsed laser sheet to generate a double exposure image on a film or CCD camera. Computer analysis of the image is used to determine the particle velocity vectors and, thus, the gas velocity within the plane of the laser sheet. Our current experiment uses PIV for measuring relative droplet gas-phase velocities in a parabolic flight environment. The results show successful application of PLIF relative to luminosity and radical emission near 308 nm. PIV results are less successful due to gas thermal expansion deflecting the seed particles away from the measurement volume. PIV is applicable for measurements in the absence of combustion.

Winter, Michael↗

Nonadiabatic dynamics of photoexcited thiopyridone isomers: An interplay between El-Sayed’s conditions and energy gap law

We investigated the non-adiabatic dynamics of photoexcited thiopyridone systems across their ortho-, meta-, and para-isomeric forms. The relaxation pathways of the three isomers in both gas phase and solvent environments are mapped using surface hopping dynamics based on time-dependent density functional theory. Our analysis highlights the influence of isomeric structures on photophysical behavior, offering insights into design principles to control photochemical phenomena. The simulations suggest a systematic reduction in the rate of intersystem crossing (ISC) from ortho- to meta- to para-isomer. Comparisons with multiconfigurational wave function methods in the gas phase further demonstrate how electronic structure influences the predicted dynamical pathways. The simulated dynamics demonstrates that the spin–orbit coupling strength alone does not determine the rate of ISC, as both state energetics and underlying electronic and structural features play decisive roles. These aspects explain the much slower ISC in the para-isomer, as well as the non-negligible role of the El-Sayed forbidden pathway in the computed ISC dynamics.

Complete-active space self-consistent field↗

Explosive desorption of icy grain mantles in dense clouds

The cycling of the condensible material in dense clouds between the gas phase and the icy grain mantles is investigated. In the model studied, desorption of the ice occurs due to grain mantle explosions when photochemically stored energy is released after transient heating by a cosmic ray particle. It is shown that, depending on the grain size distribution in dense clouds, explosive desorption can maintain up to about eight percent of the carbon in the form of CO in the gas phase at typical cloud densities.

Schutte, W. A.↗

Numerical Study of the Transient Vaporization of an Oxygen Droplet at Sub- and Super-Critical Conditions

Unsteady vaporization of a droplet in a high-pressure quiescent environment has been studied. With spherical symmetry and constant pressure, the process is diffusion controlled. At low pressures droplet heating is significant for most of the droplet lifetime, and an unsteady analysis of the gas phase is required. Then, the vaporization of a liquid oxygen droplet in gaseous hydrogen at moderate and high pressures is considered. At super-critical pressures, the surface temperature reaches the computed critical mixture value where a model for super-critical combustion is needed. The details of the diffusion layer of dissolved hydrogen do not significantly affect the results. Various methods are explored to compute the gas-phase density. Under the model's assumptions, homogeneous nucleation is not likely to occur.

Delplanque, J.-P.↗

A FIB/TEM/Nanosims Study of a Wark-Lovering Rim on an Allende CAI

Ca- Al-rich inclusions (CAIs) are commonly surrounded by Wark-Lovering (WL) rims - thin (approx. 50 micrometers) multilayered sequences - whose mineralogy is dominated by high temperature minerals similar to those that occur in the cores of CAIs [1]. The origins of these WL rims involved high temperature events in the early nebula such as condensation, flashheating or reaction with a nebular reservoir, or combinations of these processes. These rims formed after CAI formation but prior to accretion into their parent bodies. We have undertaken a coordinated mineralogical and isotopic study of WL rims to determine the formation conditions of the individual layers and to constrain the isotopic reservoirs they interacted with during their history. We focus here on the spinel layer, the first-formed highest- temperature layer in the WL rim sequence. Results and Discussion: We have performed mineralogical, chemical and isotopic analyses of an unusual ultrarefractory inclusion from the Allende CV3 chondrite (SHAL) consisting of an approx. 500 micrometers long single crystal of hibonite and co-existing coarsegrained perovskite. SHAL is partially surrounded by WL rim. We previously reported on the mineralogy, isotopic compositions and trace elements in SHAL [2-4]. The spinel layer in the WL rim is present only on the hibonite and terminates abruptly at the contact with the coarse perovskite. This simple observation shows that the spinel layer is not a condensate in this case (otherwise spinel would have condensed on the perovskite as well). The spinel layer appears to have formed by gas-phase corrosion of the hibonite by Mg-rich vapors such that the spinel layer grew at the expense of the hibonite. We also found that the spinel layer has the same 16Orich composition as the hibonite. The spinel layer is polycrystalline and individual crystals do not show a crystallographic relationship with the hibonite. An Al-diopside layer overlies the spinel layer, and is present on both the hibonite and perovskite. While the spinel is 16O-rich, WL-rim perovskite and pyroxene are 16O-poor. This isotopic heterogeneity likely reflects O isotopic equilibration of WL-rim perovskite and pyroxene with a planetary O isotopic reservoir after the WL rim formation. The hibonite is zoned and contains wt.% levels of Ti, Mg and Fe in contact with the Fe-bearing spinel (Sp60Hc40) in the WL rim. The Fe enrichment in spinel is likely related to the Na-Fe metasomatism that is ubiquitous in Allende. Conclusions: The petrography and microstructure of the spinel layer in a WL rim sequence shows that it formed by gas phase reactions at high temperature in the nebula. The oxygen isotopic composition of the spinel indicates that this WL rim layer formed in the same (or similar) nebular gas reservoir as the host CAI.

Keller, L. P.↗