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At least 559 records · Page 31

Semiclassical study of the quenching of excited-state fluorine atom by hydrogen molecule - Comparison between reactive and nonreactive processes

Semiclassical calculations are carried out for the quenching of excited-state fluorine atom by collinear collisions with hydrogen molecule. The overall quenching probability is the sum of two contributions: the reactive quenching probability associated with the formation of hydrogen fluoride and the nonreactive quenching probability leading to ground-state fluorine atom and hydrogen molecule. The reactive probability is greater in the threshold region of the collision energy, whereas the nonreactive probability dominates for energies above the threshold region.

Yuan, J.-M.↗

Reactivity of pyrylium salts toward basic reactants

The reactivity of some N-acyl and N-sulfonyl-hydrazines 2-4, 10a-10g, 12, 13, 16a, 16b and of hydrazones 18, benzyldihydrazone 21 towards pyrylium salts 1 was examined. By reaction of 2,4,6-trimethyl-pyrylium salt 1 with substituted hydrazines some pyridinium salts were obtained. Relationships between basicity and reactivity were discussed.

Neidlein, R.↗

A flow-system comparison of the reactivities of calcium superoxide and potassium superoxide with carbon dioxide and water vapor

A single pass flow system was used to test the reactivity of calcium superoxide with respiratory gases and the performance was compared to that of potassium superoxide. The KO2 system is used by coal miners as a self-contained unit in rescue operations. Particular attention was given to the reactivity with carbon dioxide and water vapor at different temperatures and partial pressures of oxygen, carbon dioxide, and water vapor. The calcium superoxide beds were found to absorb CO2 and H2O vapor, releasing O2. The KO2 bed, however, released O2 at twice the rate of CO2 absorption at 37 C. It is concluded that the calcium superoxide material is not a suitable replacement for the KO2 bed, although Ca(O2)2 may be added to the KO2 bed to enhance the CO2 absorption.

Wood, P. C.↗

Acid dew and the role of chemistry in the dry deposition of reactive gases to wetted surfaces

A formalism is developed to describe the dry deposition of soluble reactive gases to wetted surfaces in terms of the relevant meteorological conditions, the surface roughness, the total amount of liquid water present on the surface, the rate of accumulation of this water, and the species' solubility and reactivity in the surface water. This formulation is then incorporated into a model designed to simulate the generation of acidic dew from the deposition of HNO3, SO2, S(IV) oxidants, H2O2, and O3. Similar to the observations of dew in the continental U.S., the model generates a dewdrop pH of about 4 by the end of the night; the pH can rapidly fall to toxic levels due to rapid evaporation after sunrise. Relatively low deposition velocities are predicted for the SO2 and O3 because of their lower solubilities and hence larger surface resistances than those of the other oxidants. Because the chemical lifetime of the SO2 in the dew is influenced by the atmospheric levels of H2O2, O3, and SO2, the SO2 deposition velocity is a strong function of these species' atmospheric abundances.

Chameides, William L.↗

CuInSe2/ZnSe solar cells using reactively sputter-deposited ZnSe

Results on CuInSe2/ZnSe thin-film heterojunction photovoltaic devices are presented. By the use of reactive magnetron cosputtering of Zn and In dopant in Ar/H2Se, ZnSe thin films have been deposited on glass and conducting SnO2-coated glass substrates with resistivity as low as 20 ohm-cm at deposition temperatures as low as 120 C. Preliminary ZnSe depositions onto CuInSe2 films supplied by industrial laboratories are encouraging. Reactive-sputter-deposition parameters for ZnSe have yet to be optimized for CuInSe2 substrates; however, open-circuit voltages as high as 430 mV were obtained. The highest short-circuit current density, as determined by spectral response weighted for AM1.5 global insulation, was 37.4 mA/sq cm. In all cases, a highly conductive ZnO film was overcoated onto the ZnSe to reduce the overall sheet resistance.

Nouhi, A.↗

Measurements of NO and total reactive odd-nitrogen, NOy, in the Antarctic stratosphere

Measurements of NO and total reactive N, NOy, were made as part of the Airborne Antarctic Ozone Experiment conducted in Punta Arenas, Chile during Aug. and Sept. 1987. The total reactive N reservoir includes the species NO, NO2, NO3, N2 O5, HNO3, and ClONO2. The instrument was located on board the NASA ER2 aircraft which conducted 12 flights over the Antarctic continent reaching altitudes of 18 km at 72 deg S latitude. The NOy technique utilized the conversion of component NOy species to NO on a gold catalyst and the subsequent detection of NO by the chemiluminescence reaction of NO with ozone. Since the inlet sample line is heated and the catalyst operates at 300 C, NOy incorporated in aerosols evaporates and is converted to NO. NO was measured on two separate flights by removing the catalyst from the sample inlet line.

Fahey, D. W.↗

On the development of a reactive sensor-based robotic system

Flexible robotic systems for space applications need to use local information to guide their action in uncertain environments where the state of the environment and even the goals may change. They have to be tolerant of unexpected events and robust enough to carry their task to completion. Tactical goals should be modified while maintaining strategic goals. Furthermore, reactive robotic systems need to have a broader view of their environments than sensory-based systems. An architecture and a theory of representation extending the basic cycles of action and perception are described. This scheme allows for dynamic description of the environment and determining purposive and timely action. Applications of this scheme for assembly and repair tasks using a Universal Machine Intelligence RTX robot are being explored, but the ideas are extendable to other domains. The nature of reactivity for sensor-based robotic systems and implementation issues encountered in developing a prototype are discussed.

Hexmoor, Henry H.↗

Quantum mechanical algebraic variational methods for inelastic and reactive molecular collisions

The quantum mechanical problem of reactive or nonreactive scattering of atoms and molecules is formulated in terms of square-integrable basis sets with variational expressions for the reactance matrix. Several formulations involving expansions of the wave function (the Schwinger variational principle) or amplitude density (a generalization of the Newton variational principle), single-channel or multichannel distortion potentials, and primitive or contracted basis functions are presented and tested. The test results, for inelastic and reactive atom-diatom collisions, suggest that the methods may be useful for a variety of collision calculations and may allow the accurate quantal treatment of systems for which other available methods would be prohibitively expensive.

Schwenke, David W.↗

Reactive iron in marine sediments

The influence of reactive iron oxides on sediment pore-water chemistry is considered in detail. A carefully calibrated extraction scheme is used to determine the depth distributions of reactive iron phases at two very different localities: the relatively iron-rich Mississippi Delta and the relatively iron-poor FOAM site in Long Island Sound. Closed system incubations are used to characterize the rates of reaction between sulfide and both naturally occurring and pure iron mineral phases. Rates of iron liberation to pore solution are measured in the presence and absence of sulfate reduction, and the origin of dissolved iron in organic-rich sediments is speculated upon.

Canfield, Donald E.↗

Evidence for Phanerozoic reactivation of the Najd Fault System in AVHRR, TM, and SPOT images of central Arabia

SPOT stereoscopic and TM multispectral images support evidence in AVHRR thermal-IR images of a major unmapped shear zone in Phanerozoic cover rocks southeast of the ancient Najd Fault System in the Arabian Shield. This shear zone and faults of the Najd share a common alignment, orientation, and sinistral sense of movement. These similarities suggest a 200-km extension of the Najd Fault System and reactivation since it formed in the late Precambrian. Topographic and lithologic features in the TM and SPOT data along one of three faults inferred from the AVHRR data indicate sinistral offsets up to 2.5 km, en echelon folds and secondary faults like those predicted by models of left-lateral strike-slip faulting. The age of the affected outcrops indicates reactivation of Najd faults in the Cretaceous, judging from TM and SPOT data or in the Tertiary, based on AVHRR data. The total length of the system visible at the surface measures 1300 km. If the Najd Fault System is extrapolated beneath sands of the Empty Quarter to faults of a similar trend in South Yemen, the shear zone would span the Arabian Plate. Furthermore, if extensions into the Arabian Sea bed and into Egypt proposed by others are considered, it would exceed 3000 km.

Andre, Constance G.↗

Relative merits of reactive and forward-look detection for wind-shear encounters during landing approach for various microburst escape strategies

The goal was to quantify the benefits of airborne forward-look windshear detection and to develop and test a candidate set of strategies for recovery from inadvertent microburst encounters during the landing approach, given the utilization of both reactive-only and forward-look windshear detection. Candidate strategies were developed and evaluated using a non-piloted simulation consisting of a simple point-mass performance model of a transport-category airplane flying through an analytical microburst model. The results indicate that the factor which most strongly effects a microburst recovery is the time at which the recovery is initiated. Forward-look alerts given 10 seconds prior to microburst entry permitted recoveries to be made with negligible altitude loss. The results also show that no single microburst scenario can be used to evaluate the relative merits of various recovery strategies. The type of alert used to initiate the recovery (reactive or forward-look) and the altitude of the microburst encounter had an effect on the type of recovery strategy that performed best. These factors may have serious implications for the design and certification of windshear systems.

Hinton, David A.↗

Reactive behavior, learning, and anticipation

Reactive systems always act, thinking only long enough to 'look up' the action to execute. Traditional planning systems think a lot, and act only after generating fairly precise plans. Each represents an endpoint on a spectrum. It is argued that primitive forms of reasoning, like anticipation, play an important role in reducing the cost of learning and that the decision to act or think should be based on the uncertainty associated with the utility of executing an action in a particular situation. An architecture for an adaptable reactive system is presented and it is shown how it can be augmented with a simple anticipation mechanism that can substantially reduce the cost and time of learning.

Whitehead, Steven D.↗

Time-dependent wave-packet method for the complete determination of S-matrix elements for reactive molecular collisions in three dimensions

An alternative time-dependent wave-packet method for treating three-dimensional gas phase reactive atom-diatom collisions is presented. The method employs a nonreactive body-frame wave packet propagation procedure, made possible by judicious use of absorbing optical potentials, a novel scheme for interpolating the wave function from coordinates in one arrangement to those in another and the fact that the time-dependent Schroedinger equation is an initial-value problem. The last feature makes possible a computationally viable and accurate procedure for changing from one arrangement's coordinates to another. In addition, the method allows the determination of S-matrix elements over a wide range of energies from a single wave-packet propagation. The method is illustrated by carrying out detailed calculations of inelastic and reactive scattering in the H + H2 system using the Liu-Siegbahn-Truhlar-Horowitz potential surface.

Judson, Richard S.↗

Measurements of reactive nitrogen oxides (NO/y/) within and above a tropical forest canopy in the wet season

Measurements of ambient concentrations of reactive nitrogen oxides were made in the Amazon rain forest, near Manaus, Brazil, continuously at 39 m (above the canopy), and on several days and nights at 19 m (within the canopy). Concentrations were very low, typically 100-700 pptv, except for brief periods when up to 5000 pptv of NO(y) was observed, indicating polluted air from the urban area of Manaus. The forest was a net sink for NO(y) with the NO(y) flux = -7.6 + or - 5.0) x 10 to the 9th molecules/sq cm per sec in unpolluted periods, even though soils emitted NO at a significant rate (8.9 + or - 1.5 x 10 to the 9th molecules/sq cm per sec). The deposition rate for NO(y) appeared to be much larger during the daytime than at night, suggesting that uptake was controlled either by plant processes (stomatal opening) or by supply of reactive components of NO(y) (e.g., HNO3) during the daytime. Implications for regional and global atmospheric chemistry are discussed.

Bakwin, Peter S.↗

Reactivity of pi-complexes of Ti, V, and Nb towards dithioacetic acid: Synthesis and structure of novel metal sulfur-containing complexes

In order to use sulfur-containing resources economically and with minimal environmental damage, it is important to understand the desulfurization processes. Hydrodesulfurization, for example, is carried out on the surface of a heterogeneous metal sulfide catalyst. Studies of simple, soluble inorganic systems provide information regarding the structure and reactivity of sulfur-containing compounds with metal complexes. Further, consistent with recent trends in materials chemistry, many model compounds warrant further study as catalyst precursors. The reactivity of low-valent organometallic sandwich pi-complexes toward dithiocarboxylic acids is described. For example, treatment of bisbenzene vanadium with CH3CSSH affords a divanadium tetrakis(dithioacetate) complex. The crystallographically determined V-V bond distance, 2.800(2), is nearly the same as the V-V bond distance in a V(mu-nu squared-S2)2V' unit in the mineral patonite (VS4)n. The stability of the V2S4 core in the dimer is demonstrated by evidence of V2S4(+) in the mass spectrum (70 eV, solid probe) of the vanadium dimer. Several other systems relevant to HDS catalysis are also discussed.

Duraj, Stan A.↗

The influence of polar heterogeneous processes on reactive chlorine at middle latitudes - Three dimensional model implications

Three-dimensional model calculations with the NASA/GSFC chemistry and transport model have been designed to consider the impact of heterogeneous processes occurring on polar stratospheric clouds (PSCs) in the Arctic vortex on the HCl distribution. By examining the HCl concentration for a calculation with PSCs relative to a calculation with gas phase chemistry only, the impact of polar processing on reactive chlorine species at middle latitudes is inferred. Results from the chemistry and transport model reproduce basic features of the ClO measurements (Toohey et al., 1991), which were made on the ferry flights of the ER-2 from Stavanger, Norway to Moffett Field, California via Wallops Island, Virginia on February 20 and 21, 1989. The model indicates that perturbed air which is contained within the polar vortex during winter is not homogeneously mixed, and that the ferry flights were made through air with the largest conversion of HCl to reactive chlorine that is seen at middle latitudes.

Douglass, Anne R.↗

Recent spectroscopic findings concerning clay/water interactions at low humidity: Possible applications to models of Martian surface reactivity

A feasibility study assessing the utility of the adaptation of near infrared correlation spectroscopy to quantifying iron and adsorbed water in some clay-based Mars soil analog materials (MarSAM's). The work was intended to constitute Phase 1 of an approach to identifying optical analytical wavelength regions, not only for important mineral classes, but for chemically active centers within them. Many of these centers are common to unrelated mineral classes and of disproportionate influence relative to the mineral structure as a whole in determining the surface reactivity of mineral surfaces. We previously reported linearity between reflectance and total iron and total moisture over a large range of both key variables. We also discovered interesting relationships between the intensity of iron bands and the relative humidity of the systems. These relationships were confirmed. We also show that, in the low humidity range, reflectance is linearly dependent on a different kind of water from that best representing the full humidity range (the kind of water associated, in clays, with surface acidity). These relationships and the sensitivity and capability of quantitation of near infrared data indicate high promise with the production of reactive surface intermediates of products of surface reactions.

Coyne, L.↗

Inelastic and reactive scattering of hyperthermal atomic oxygen from amorphous carbon

The reaction of hyperthermal oxygen atoms with an amorphous carbon-13 surface was studied using a modified universal crossed molecular beams apparatus. Time-of-flight distributions of inelastically scattered O-atoms and reactively scattered CO-13 and CO2-13 were measured with a rotatable mass spectrometer detector. Two inelastic scattering channels were observed, corresponding to a direct inelastic process in which the scattered O-atoms retain 20 to 30 percent of their initial kinetic energy and to a trapping desorption process whereby O-atoms emerge from the surface at thermal velocities. Reactive scattering data imply the formation of two kinds of CO products, slow products whose translational energies are determined by the surface temperature and hyperthermal (Approx. 3 eV) products with translational energies comprising roughly 30 percent of the total available energy (E sub avl), where E sub avl is the sum of the collision energy and the reaction exothermicity. Angular data show that the hyperthermal CO is scattered preferentially in the specular direction. CO2 product was also observed, but at much lower intensities than CO and with only thermal velocities.

Minton, Timothy K.↗