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At least 109 records · Page 6

OH measurement by laser light absorption

Since the first attempt to measure atmospheric hydroxyl radicals by optical absorption in 1975 (Perner et al., 1976) this method has been continuously developed further and its major obstacles and limitations are known today. The laser beam needs to be expanded in order to reduce the beam divergence. At the same time the energy density of the laser beam which produces OH via ozone photolysis is reduced to such an extent that the self-produced OH concentration ranges well below the atmospheric value. Atmospheric absorptions should be observed over a wide spectral range so that not only the OH radicals are properly identified by several rotational lines but their absorption can be corrected for interfering absorptions from other air constituents as SO2, CH2O, CS2, etc., which can be identified in a wide spectral range with more confidence. Air turbulence demands fast spectral scanning or probing on and off the absorption line. Energy requirements should be kept small in field operations. In the experiment frequency doubled dye laser pulses at 308 nm are produced. The picosecond light pulses are expected to show a smooth profile (light intensity against wavelength) which will be broadened to the required spectral width according to the uncertainty principle. The pump laser will be an optoacoustically modulated Nd:YAG laser.

Perner, D.↗

Trace gas measurements from tethered balloon platforms

Instrumentation and chemical sampling and analysis procedures are described for making measurements of atmospheric carbon disulfide in the concentration range 1-1000 pptv from tethered balloon platforms. Results of a study on the CS2 composition of air downward of a saltwater marsh are reported. A method for obtaining the necessary data for solving the budget equations for surface fluxes, chemical formation rates and chemical destruction rates using data acquired from tethered balloon platforms is presented.

Bandy, Alan R.↗

A rotational-state population analysis of the high-resolution IUE observation of CS emission in comet P/Halley

The high resolution spectrum of comet P/Halley has been measured in the region of the CS emission. CS in comet Halley is produced by photodissociation of CS2 and subsequently reexcited by broad band solar radiation. An inversion procedure is introduced to extract the rotational population distribution from the dispersed fluorescence spectrum. Intensity anomalies in the wavelength region corresponding to P and Q branch emission are considered.

Prisant, M. G.↗

IUE observations of comets P/Brorsen-Metcalf and Okazaki-Levy-Rudenko

Comet P/Brorsen-Metcalf (1989c) was observed with the International Ultraviolet Explorer (IUE) on several dates from 27 July 1989 through 5 August 1989; comet Okazaki-Levy-Rudenko (1989r) was observed in low dispersion with IUE on 2 and 22 December 1989. The water production rates for P/Brorsen-Metcalf were derived from OH measurements using the vectorial model of Festou (1981). Included also are the water production rates for Okazaki-Levy-Rudenko. Two estimates of the water production rate from the O I emission around 1304 A(octogons) are included. The ultraviolet continuum was not reliably measurable in comet P/Brorsen-Metcalf in most of the spectra, but Afp is approximately 30 cm for 2 August. For the comet Okazaki-Levy-Rudenko, an Afp = 50 cm was derived for 22 December. Both comets have very little dust compared to other recently observed comets. The ratio of CS to water production rates are presented. Relative to water, both comets had less CS than P/Halley in the same range of heliocentric distances. The CS production rates were obtained from a Haser model, assuming a short-lived parent (CS2). Because the dynamic range of the IUE spectrographs are limited, not all species can be measured in each spectrum. The P/Brorsen-Metcalf spectra from 31 July and 3 August were obtained from the NSSDC Archives. Due to the observing technique used for these spectra, the exposure time and hence, the brightnesses and derived quantities have a small uncertainty associated with them.

Roettger, E. E.↗

Airborne sulfur trace species intercomparison campaign: Sulfur dioxide, dimethylsulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide

Results from an airborne intercomparison of techniques to measure tropospheric levels of sulfur trace gases are presented. The intercomparison was part of the NASA Global Tropospheric Experiment (GTE) and was conducted during the summer of 1989. The intercomparisons were conducted on the Wallops Electra aircraft during flights from Wallops Island, Virginia, and Natal, Brazil. Sulfur measurements intercompared included sulfur dioxide (SO2), dimethylsulfide (DMS), hydrogen sulfide (H2S), carbon disulfide (CS2), and carbonyl sulfide (OCS). Measurement techniques ranged from filter collection systems with post-flight analyses to mass spectrometer and gas chromatograph systems employing various methods for measuring and identifying the sulfur gases during flight. Sampling schedules for the techniques ranged from integrated collections over periods as long as 50 minutes to one- to three-minute samples every ten or fifteen minutes. Several of the techniques provided measurements of more than one sulfur gas. Instruments employing different detection principles were involved in each of the sulfur intercomparisons. Also included in the intercomparison measurement scenario were a host of supporting measurements (i.e., ozone, nitrogen oxides, carbon monoxide, total sulfur, aerosols, etc.) for purposes of: (1) interpreting results (i.e., correlation of any noted instrument disagreement with the chemical composition of the measurement environment); and (2) providing supporting chemical data to meet CITE-3 science objectives of studying ozone/sulfur photochemistry, diurnal cycles, etc. The results of the intercomparison study are briefly discussed.

Gregory, Gerald L.↗

Thermodynamic models of the chemistry of lunar volcanic gases

Thermodynamic models and mass-balance arguments are used to constrain the chemistry of lunar volcanic gases. The results predict that lunar gases were dominated by reduced C and S gases such as CO, COS, CS2, S2. The more oxidized gases CO2 and SO2 were also important, but only in limited temperature ranges. Gases such as Cl2, CCl4, and CF4 were more abundant than HF and HCl, which were the two major H compounds in the lunar gases. Chlorides and fluorides were important species for transporting many volatile and ore-forming metals, and the implications for fractionating and concentrating metals into lunar ore-deposits merit further study.

Fegley, Bruce, Jr.↗

Synthesis, vapor growth, polymerization, and characterization of thin films of novel diacetylene derivatives of pyrrole. The use of computer modeling to predict chemical and optical properties of these diacetylenes and poly(diacetylenes)

In the present work two diacetylene derivatives of pyrrole which are predicted by semiempirical AM1 calculations to have very different properties, are synthesized; the polymerizability of these diacetylenes in the solid state is determined, and the results are compared to the computer predictions. Diacetylene 1 is novel in that the monomer is a liquid at room temperature; this may allow for the possibility of polymerization in the liquid state as well as the solid state. Thin poly(diacetylene) films are obtained from compound 1 by growing films of the monomer using vapor deposition and polymerizing with UV light; these films are then characterized. Interestingly, while the poly(diacetylene) from 1 does not possess good nonlinear optical properties, the monomer exhibits very good third-order effects (phase conjugation) in solution. Dilute acetone solutions of the monomer 1 give intensity-dependent refractive indices on the order of 10 exp -6 esu; these are 10 exp 6 times better than for CS2.

Paley, M. S.↗

Nonlinear optical parameters of 7-prime,7-prime-dicyano-7-prime-apo-beta-carotene in hexane by self-action techniques

Quantitative measurements of the nonlinear refractive index coefficient n(2) and the third-order nonlinear susceptibility chi(3) for a solution of 7-prime,7-prime-dicyano-7-prime-apo-beta-carotene (DCAC) in hexane have been measured at different concentrations. The measurements have been performed by both the self-trapping and self-phase modulation techniques using a CW Ar(+) laser. The results show that DCAC has a relatively large nonlinearity, attributed to a thermal mechanism, with n(2) of the order of 10 exp 9 times that of CS2.

Abdeldayem, Hossin A.↗

Emissions of sulfur gases from marine and freshwater wetlands of the Florida Everglades - Rates and extrapolation using remote sensing

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of over 500 nmol/sq m/h occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of about 60 nmol/sq m/h, which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat TM were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emissions were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities accounted for about 24 percent of the total S emissions.

Hines, Mark E.↗

Emissions of biogenic sulfur gases from Alaskan tundra

Fluxes of the biogenic sulfur gases carbonyl sulfide (COS), dimethyl sulfide (DMS), methyl mercaptan (MeSH), and carbon disulfide (CS2) were determined for several freshwater and coastal marine tundra habitats using a dynamic enclosure method and gas chromatography. In the freshwater tundra sites, highest emissions, with a mean of 6.0 nmol/m(sup -2)H(sup -1) (1.5-10) occurred in the water-saturated wet meadow areas inhabited by grasses, sedges, and Sphagnum mosses. In the drier upland tundra sites, highest fluxes occurred in areas inhabited by mixed vegetation and labrador tea at 3.0 nmol/m(sup -2)h(sup -1) (0-8.3) and lowest fluxes were from lichen-dominated areas at 0.9 nmol/m(sup -2)h(sup -1). Sulfur emissions from a lake surface were also low at 0.8 nmol/m(sup -2)h(sup -1). Of the compounds measured, DMS was the dominant gas emitted from all of these sites. Sulfure emissions from the marine sites were up to 20-fold greater than fluxes in the freshwater habitats and were also dominated by DMS. Emissions of DMS were highest from intertidal soils inhabited by Carex subspathacea (150-250 nmol/m(sup -2)h(sup -1)). This Carex sp. was grazed thoroughly by geese and DMS fluxes doubled when goose feces were left within the flux chamber. Emissions were much lower from other types of vegetation which were more spatially dominant. Sulfure emissions from tundra were among the lowest reported in the literature. When emission data were extrapolated to include all tundra globally, the global flux of biogenic sulfur from this biome is 2-3 x 10(exp 8) g/yr. This represents less than 0.001 percent of the estimated annual global flux (approximately 50 Tg) of biogenic sulfur and less than 0.01 percent of the estimated terrestrial flux. The low emissions are attributed to the low availability of sulfate, certain hydrological characteristics of tundra, and the tendency for tundra to accumulate organic matter.

Hines, Mark E.↗

Emissions of sulfur gases from marine and freshwater wetlands of the Florida Everglades: Rates and extrapolation using remote sensing

Rates of emissions of the biogenic sulfur (S) gases carbonyl sulfide (COS), methyl mercaptan (MSH), dimethyl sulfide (DMS), and carbon disulfide (CS2) were measured in a variety of marine and freshwater wetland habitats in the Florida Everglades during a short duration period in October using dynamic chambers, cryotrapping techniques, and gas chromatography. The most rapid emissions of greater than 500 nmol/m(sup -2)h(sup -1) occurred in red mangrove-dominated sites that were adjacent to open seawater and contained numerous crab burrows. Poorly drained red mangrove sites exhibited lower fluxes of approximately 60 nmol/m(sup -2)h(sup -1) which were similar to fluxes from the black mangrove areas which dominated the marine-influenced wetland sites in the Everglades. DMS was the dominant organo-S gas emitted especially in the freshwater areas. Spectral data from a scene from the Landsat thematic mapper were used to map habitats in the Everglades. Six vegetation categories were delineated using geographical information system software and S gas emission were extrapolated for the entire Everglades National Park. The black mangrove-dominated areas accounted for the largest portion of S gas emissions to the area. The large area extent of the saw grass communities (42 percent) accounted for approximately 24 percent of the total S emissions.

Hines, Mark E.↗

Emissions of sulfur gases from wetlands

Data on the emissions of sulfur gases from marine and freshwater wetlands are summarized with respect to wetland vegetation type and possible formation mechanisms. The current data base is largest for salt marshes inhabited by Spartina alterniflora. Both dimethyl sulfide (DMS) and hydrogen sulfide (H2S) dominate emissions from salt marshes, with lesser quantities of methyl mercaptan (MeSH), carbonyl sulfide (COS), carbon disulfide (CS2) and dimethyl disulfide (DMDS) being emitted. High emission rates of DMS are associated with vegetation that produces the DMS precursor dimethylsulfonionpropionate (DMSP). Although large quantities of H2S are produced in marshes, only a small percentage escapes to the atmosphere. High latitude marshes emit less sulfur gases than temperate ones, but DMS still dominates. Mangrove-inhabited wetlands also emit less sulfur than temperate S. alterniflora marshes. Few data are available on sulfur gas emissions from freshwater wetlands. In most instances, sulfur emissions from temperate freshwater sites are low. However, some temperate and subtropical freshwater sites are similar in magnitude to those from marine wetlands which do not contain vegetation that produces DMSP. Emissions are low in Alaskan tundra but may be considerably higher in some bogs and fens.

Hines, Mark E.↗

A real-time prediction of UTC

The reference time scale for all scientific and technologic applications on the Earth, the Universal Coordinated Time (UTC), must be as stable, reliable, and accurate as possible. With this in view the BIPM and before it the BIH, have always calculated and then disseminated UTC with a delay of about 80 days. There are three fundamental reasons for doing this: (1) It takes some weeks for data, gathered from some 200 clocks spread world-wide, to be collected and for errors to be eliminated; (2) changes in clock rates can only be measured with high precision well after the fact; and (3) the measurement noise originating in time links, in particular using Loran-C, is smoothed out only when averaging over an extended period. Until mid-1992, the ultimate stability of UTC was reached at averaging times of about 100 days and corresponded to an Allan deviation sigma(sub y)(tau) of about 1,5x10(exp -14) then compared to the best primary clock in the world, the PTB CS2. For several years now, a predicted UTC has been computed by the USNO through an extrapolation of the values as published in deferred time by the BIPM. This is made available through the USNO Series 4, through the USNO Automated Data Service, and through GPS signals. Due to the instability of UTC, the poor predictability of the available clocks, and the intentional SA degradation of GPS signals, the real-time access to this extrapolated UTC has represented the true deferred-time UTC only to within several hundreds of nanoseconds.

Thomas, Claudine↗

Photodissociation Cross Sections for the Production of C2 from C2H Using Laser Induced Hg Photosensitization and Tunable Ultraviolet and Visible Lasers

The principle goal of our research was to understand the formation of free radicals in comets. To do this we compared laboratory results with cometary observations in attempt to make sure that the cometary observations agree with what is known about the photochemistry of the proposed parent molecule. Initially we concentrated on the CS emission in an effort to show the parent of this molecule was CS2, consistent with cometary observations of the photochemical lifetime. We then started to look into the problem of the C2 formation in comets. We set out to see if we could measure all of the nascent distributions of the C2 products in the hope that they would be a characteristic signature of the formation process.

Jackson, William M.↗

Atmospheric Sulfur Cycle Effects of Carbonyl Sulfide (OCS)

Carbonyl Sulfide(OCS) is considered to be one of the major sources of sulfur appearing in the stratosphere due to its relative inertness, about I to 10 yearsl. However, the roles of OCS as well as other reduced sulfur compounds such as carbon disulfide (CS2), hydrogen sulfide (H2S), and dimethyl disulfide(CH3)2S2, are not completely understood in the atmosphenc sulfur cycle. Consequently vely little information is available about the effect of sulfur compounds in the stratosphere. The ability of OCS to penetrate into the stratosphere makes it an excellent tracer for study of the role of the sulfi r cycle in stratospheric chemistry. Previously techniques such as gas chromatography and whole air sampling have been used to measure OCS analytically. Each technique had its drawbacks however, with both being quite slow, and whole air sampling being somewhat unreliable. With molecular spectroscopy, however, it has been found in recent years that the tunable diode laser absorption spectrometer (TDL) provides a very rapid and accurate method of measuring OCS and other trace gases

McBee, Joshua↗

High-Resolution Temperature-Dependent Photoabsorption Cross Section Measurements of S2, with Application to HST UV Spectra of SL9/Jupiter

The Hubble Space Telescope (HST) UV spectra of Jupiter after the collision of Comet SL9 show predominantly molecular features of S2, CS2, NH3, and H2S in the 1800-3200 A region. The HST observations were made under various phases of impact conditions which gave temperatures higher than 1000 K. It is thus clear that temperature-dependent laboratory cross section data are required in order to determine the molecular abundances in Jupiter's atmosphere after the impact of Comet Shoemaker-Levy 9. The required high-resolution temperature dependent S2 absorption cross sections have not been directly measured in the laboratory. To provide the required data for modelers our objective is to accurately measure the high-resolution (FWHM = 0.003 A) and medium resolution (FWHM - 0.08 A) temperature dependent S2 in the 2450-3200 A region. Using the experimental setup we have obtained absorbtion spectra of S2 under various temperature conditions.

Wu, C. Y. Robert↗

Improved Chromatographic Techniques for Sulfur Pollutants

This paper describes several improvements in instrumental techniques for the analysis of low ppb concentrations of sulfur gases using gas chromatography (G.C.). This work has focused on the analytical problem of ambient air monitoring of the two main sulfur gas pollutants, hydrogen sulfide and sulfur dioxide. The most significant technical improvement that will be reported here is the newly developed silica gel column for ppb concentrations of the light sulfur gases (COS, H2S, CS2, SO2, CH3SH). A simplified inlet system will be described which improves reliability of the GC system. The flame photometric detector is used as the means of selectively and sensitively detecting the low concentrations of sulfur gases. Improvements will be described which have yielded better performance than previously reported for this application of the detector. Also included in this paper will be a report of field monitoring using this improved GC system. Reliability and repeatability of performance at the low ppb concentrations of sulfur gases will be demonstrated.

Hartmann, C. H.↗

Dynamics of the Impacts

The SL9 impacts are best known by their plumes, several of which were imaged towering 3000 km above Jupiter's limb. The heat released when they fen back on the atmosphere produced the famous infrared main events. The reentry shock was observed directly in CO emission and indirectly through thermally glowing dust. The relatively low color temperature of the latter implies that most of the energy released on reentry was radiated. If so, the R impact released some 3 x 10(exp 26) ergs, and the larger L, K, and G impacts as much as 3 x 10(exp 27) ergs. These estimates agree well with impact energies deduced from tidal disruption computations. The duration of the infrared events measures time aloft and hence provides a second measure of plume height. These indicate that plume height was only weakly dependent on impact energy. Evidently all the plumes were launched at roughly 10-13 km/s. Using a semi-analytic model for the deceleration, disintegration, and destruction of intruding bodies by an ever-vigilant atmosphere, we find that similar plume heights is a direct consequence of smaller impactors exploding at higher altitudes, in such a way that the different explosions were geometrically similar. We then compare the predictions of our model to the Venerian cratering record, which provides a good statistical test of impact deceleration by a thick atmosphere. Chemistry should have provided an independent measure of explosion altitude: abundant shock-generated CS, CS2 and HCN indicates a source in dry jovian air, above the putative water clouds. However, the Galileo Probe results seem to imply that we should expect no more. Observed water and S2 are consistent with a somewhat oxidized gas (presumably the comet itself), but the absence of SO2 and CO2 shows that conditions were neither too oxidizing nor the shocks too hot.

Zahnle, Kevin↗