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At least 505 records · Page 28

Reaction of N2O5 with H2O on carbonaceous surfaces

The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

Brouwer, L.↗

A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction

The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

Friedl, Randall R.↗

Enhanced Raman spectroscopic study of rotational isomers on metal surfaces

Surfaced-enhanced Raman spectroscopy has been used to study rotational isomers of succinonitrile and N-methyl-thioacetamide on Cu and Ag surfaces. Both the gauche and trans conformers of succinonitrile are found to chemisorb on the metal surface. The doubly degenerate nu(C-triple bond-N) in the free molecules is removed when succinonitrile adsorbs on copper, which indicates that the two (C-triple bond-N) groups are no longer chemically equivalent. Both conformers are found to coordinate to the copper surface through the pi system of one of the two (C-triple bond-N) groups. In the case of N-methyl-thioacetamide, the population of the cis isomer is greatly increased on Cu and Ag surfaces. This is probably due to surface-induced cis-trans isomerization, in which the predominant trans isomer is converted to the cis isomer.

Loo, B. H.↗

Quantitative abundance estimates from bidirectional reflectance measurements

A simplified approach for estimating mineral abundances in mineral mixtures from bidirectional reflectance measurements is presented. Fundamental to this approach is a priori information concerning reflectance spectra of the individual minerals and an estimate of the particle sizes of the components. Simplified equations for bidirectional reflectance are used to linearize the systematics of spectral mixing. The method was used to determine the relative proportions of olivine, magnetite, enstatite, and anorthite in a mixture; the mass fractions of mixture components were calculated on the basis of known particle diameters. The results indicate that for materials without strongly adsorbing components, the accuracy of abundance determinations is better than 5 percent.

Mustard, John F.↗

International Conference on Vacuum Ultraviolet Radiation Physics, 8th, Lunds Universitet, Sweden, Aug. 4-8, 1986, Proceedings

The interactions of VUV radiation with solids are explored in reviews and reports of recent theoretical and experimental investigations from the fields of atomic and molecular physics, solid-state physics, and VUV instrumentation. Topics examined include photoabsorption and photoionization, multiphoton processes, plasma physics, VUV lasers, time-resolved spectroscopy, synchrotron radiation centers, solid-state spectroscopy, and dynamical processes involving localized levels. Consideration is given to the fundamental principles of photoemission, spin-polarized photoemission, inverse photoemission, semiconductors, organic materials, and adsorbates.

Nilsson, Per-Olof↗

An enzyme immunoassay for rat growth hormone - Applications to the study of growth hormone variants

A sensitive and specific competitive enzyme immunoassay for rat growth hormone (GH) is described and its use in the detection of GH variants is demonstrated. In the present assay, soluble GH and GH adsorbed to a solid-phase support compete for monkey anti-GH antibody binding sites. The immobilized antibody-GH complex is detected and quantified using goat antimonkey immunoglobin G covalently conjugated to horseradish peroxidase. It is noted that the assay can be performed in 27 hours and that sensitivities in the range of 0.19 to 25 ng can be obtained in the region of 10 to 90 percent binding.

Farrington, Marianne A.↗

Development of a torsion balance for adhesion measurements

A new torsion balance for study of adhesion in ceramics is discussed. A torsion wire and a linear variable differential transformer are used to monitor load and to measure pull-off force (adhesion force). The investigation suggests that this torsion balance is valuable in studying the interfacial properties of ceramics in controlled environments such as in ultrahigh vacuum. The pull-off forces measured in dry, moist, and saturated nitrogen atmosphere demonstrate that the adhesion of silicon nitride contacts remains low at humidities below 80 percent but rises rapidly above that. The adhesion at saturation is 10 times or more greater than that below 80 percent relative humidity. The adhesion in a saturated atmosphere arises primarily from the surface tension effects of a thin film of water adsorbed on the surface. The surface tension of the water film was 58 x 10 to the minus 5 to 65 x 10 to the minus 5 power. The accepted value for water is 72.7 x 10 to the minus 5 power N/cm. Adhesion characteristics of silicon nitride in contact with metals, like the friction characteristics of silicon carbide to metal contacts, can be related to the relative chemical activity of metals in ultrahigh vacuum. The more active the metal, the higher the adhesion.

Miyoshi, Kazuhisa↗

Solar generation and storage of O2 (a 1 delta g)

An investigation was performed of the technical steps required to design a solar powered oxygen-iodine laser. Singlet delta oxygen is formed upon transfer of energy from selected photoexcited dye molecules to ground state molecular oxygen and then is concentrated and stored as an endoperoxide by reaction with an aromatic hydrocarbon. The endoperoxide, when heated, releases singlet oxygen in high yield thus providing a regenerable source of laser fuel. Energy transfer from dye molecules to molecular oxygen was investigated. When dye molecules were adsorbed to polymer substrates it was observed that the dye became embedded in the polymer matrix. Porphin dyes were incorporated into films of 1,4-dimethyl-2-poly(vinylnaphthalene), 2PVN. An endoperoxide was formed when porphin-doped 2PVN was exposed to visible radiation. This demonstrates the possibility of generating singlet oxygen using solar energy and concentrating and storing it in one simple step. Transport of energy by exciton migration in polycrystalline dye films was also investigated.

Twarowski, Allen J.↗

Two puzzling aspects of protein crystal growth

A study is presented of several mechanisms which may reduce crystal growth rates and or terminate crystal growth. It is found that salt gradients which change the local chemical potential of the protein are insufficient to account for the slow crystal growth rates which have been reported. Contaminants which adsorb protein from solution may reduce the effective protein concentration, but the impurity's concentration and its affinity for protein are unknown. Association of protein molecules in bulk solution can reduce the monomer concentration significantly, but extant theory and experiment are not sensitive enough to determine the actual concentration of aggregates in solution. For systems of interest, shear-induced effects were found to be too weak to interfere with normal binding of incoming protein molecules. Although we found that most crystal growth occurs in a regime where both interfacial kinetics and diffusion influence crystal growth, the role of mass transfer rates on the terminal size of crystals is unknown, primarily because no data exist which cover the size range of interest (0.1 mm to 1 mm in length).

Grant, M. L.↗

Coadsorption of H2O and CO2 on the Martian surface

The adsorption of both CO2 and H2O was measured, under conditions of temperature and partial pressure similar to Mars, for a variety of absorbents. Both adsorb at coverages that exceed a monolayer at their respective Martian abundances. Clearly, their simultaneous presence in the Martian atmosphere will result in coadsorption of both at concentrations that may differ greatly from those measured during separate measurements. To the best of our knowledge, no data exists on the coadsorption of both gases. Co-adsorption experiments were begun and pertinent results will be reported. In the meantime the predicted behavior of such a system was mathematically explored as a compliment to the data, and to aid in its eventual interpretation.

Zent, A. P.↗

Role of minerals in thermal alteration of organic matter. II - A material balance

The paper presents the results of pyrolysis experiments which were carried out on Green River and Monterey Formation kerogens with and without calcite, illite, or montmorillonite at 300 C for 2 to 1,000 hours under dry and hydrous conditions. The data reveal significant differences in the products generated by pyrolysis of kerogens with and without minerals. Both illite and montmorillonite adsorb a considerable portion of the generated bitumen. In the case of calcite, the pyrolysis products are similar to those from kerogen heated alone, and bitumen adsorption is negligible.

Tannenbaum, Eli↗

The role of minerals in the thermal alteration of organic matter. III - Generation of bitumen in laboratory experiments

A series of pyrolysis experiments, utilizing two different immature kerogens (from the Monterey and Green River Formations) mixed with common sedimentary minerals (calcite, illite, or Na-montmorillonite), was conducted to study the impact of the mineral matrix on the bitumen that was generated. Calcite has no significant influence on the thermal evolution of bitumen and also shows virtually no adsorption capacity for any of the pyrolysate. In contrast, montmorillonite (M) and illite, to a lesser extent, alter bitumen during dry pyrolysis. M and illite also display strong adsorption capacities for the polar constituents of bitumen. By this process, hydrocarbons are substantially concentrated within the pyrolysate that is not strongly adsorbed on the clay matrices. The effects of the clay minerals are significantly reduced during hydrous pyrolysis. The strong adsorption capacities of M and illite, as well as their thermocatalytic properties, may in part explain why light oils and gases are generated from certain argillaceous source-rock assemblages, whereas heavy immature oils are often derived from carbonate source rocks.

Huizinga, Bradley J.↗

Microelectrophoretic study of calcium oxalate monohydrate in macromolecular solutions

Electrophoretic mobilities were measured for calcium oxalate monohydrate (COM) in solutions containing macromolecules. Two mucopolysaccharides (sodium heparin and chondroitin sulfate) and two proteins (positively charged lysozyme and negatively charged bovine serum albumin) were studied as adsorbates. The effects of pH, calcium oxalate surface charge (varied by calcium or oxalate ion activity), and citrate concentration were investigated. All four macromolecules showed evidence for adsorption. The macromolecule concentrations needed for reversing the surface charge indicated that the mucopolysaccharides have greater affinity for the COM surface than the proteins. Citrate ions at high concentrations appear to compete effectively with the negative protein for surface sites but show no evidence for competing with the positively charged protein.

Curreri, P. A.↗

A comparative review of optical surface contamination assessment techniques

This paper will review the relative sensitivities and practicalities of the common surface analytical methods that are used to detect and identify unwelcome adsorbants on optical surfaces. The compared methods include visual inspection, simple reflectometry and transmissiometry, ellipsometry, infrared absorption and attenuated total reflectance spectroscopy (ATR), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS), and mass accretion determined by quartz crystal microbalance (QCM). The discussion is biased toward those methods that apply optical thin film analytical techniques to spacecraft optical contamination problems. Examples are cited from both ground based and in-orbit experiments.

Heaney, James B.↗

Laboratory investigations of Mars - Chemical and spectroscopic characteristics of a suite of clays as Mars soil analogs

A model system of Mars soil analog materials (MSAMs) was prepared, and the properties of these clays, such as chemical composition, surface-ion composition, water adsorption isotherms, and reflectance spectra, were examined. The results of these studies, performed along with simulations of the Viking Labeled Release Experiement using MSAMs, indicate that surface iron and adsorbed water are important determinants of clay behavior, as evidenced by changes in reflectance, water absorption, and clay surface reactions. The paper discusses the relevance of these results to the two major questions raised by prior explorations of Mars: has there ever been abundant water on Mars, and why is the iron found in the Martian soil not readily seen in the reflectance spectra of the surface?

Banin, Amos↗

Flexible, Polymer-Filled Metallic Conductors

Procedure developed to make materials both flexible and reasonably good electrical conductors. Metal or polymer sheet substrate cleaned with beam of energetic inert-gas ions to remove adsorbed gases and contaminants from surface. After cleaning, substrate coated by cosputter deposition of both conductive metal and flexible polymer. Removed by either mechanical or chemical-dissolution technique, and resulting flexible metal/polymer conductor bonded at low temperature to conductor-surface contacts.

Banks, Bruce A.↗

Vertical O(sub 3) distribution as a diagnostic for eddy diffusion profile

A model study of the distribution of ozone on Mars is presented. It is showed that knowledge of the vertical ozone distribution, such as could be obtained from ultraviolet measurements from an orbiter, could be used to infer vertical transport rates at various levels in the atmosphere. The dependence of the vertical distribution of O(sub 3) on the height variation of eddy diffusion coefficient is illustrated. Ozone abundance is a valuable diagnostic for other climatological parameters. In addition, the sensitivity of O(sub 3) distribution to eddy diffusion may aid in determining the role of surface oxidation and recombination processes and lead to a better understanding of the volatiles released or adsorbed cyclically in the Martian regolith.

Tyler, A. L.↗

Self-actuating heat switches for redundant refrigeration systems

A dual refrigeration system for cooling a sink device is described, which automatically thermally couples the cold refrigerator to the sink device while thermally isolating the warm refrigerator from the sink device. The system includes two gas gap heat switches that each thermally couples one of the refrigerators to the sink device, and a pair of sorption pumps that are coupled through tubes to the heat switches. When the first refrigerator is operated and therefore cold, the first pump which is thermally coupled to it is also cooled and adsorbs gas to withdraw it from the second heat switch, to thereby thermally isolate the sink device from the warm second refrigerator. With the second refrigerator being warm, the second pump is also warm and desorbs gas, so the gas lies in the first switch, to close that switch and therefore thermally couple the cold first refrigerator to the sink device. Thus, the heat switches are automatically switched according to the temperature of the corresponding refrigerator.

Chung K Chan↗