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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 9248-9254 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dissociative chemisorption of nitrogen on clean and cesiated Ru(0001) surfaces has been studied using high-resolution electron energy loss spectroscopy (HREELS) and thermal desorption spectroscopy (TDS). N2 (at 300 K) chemisorbs dissociatively with a sticking coefficient of 2×10−6, independent of substrate temperature which was varied between 420 and 700 K. The saturation coverage is found at 0.5 monolayer. The energy of the N–Ru stretching vibration is 71 meV at the bare surface and 69 meV at the cesiated Ru(0001) surface. The activation energy for desorption is about 190 kJ/mol for small coverages. The kinetic data suggest the existence of an activation barrier in the entrance channel of adsorption. Preadsorption of 0.08 monolayer of Cs increases the sticking coefficient only by a factor of 1.3, and the maximum amount of adsorbed N is reduced due to blocking of adsorption sites through Cs.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 9977-9985 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dynamic behavior of elliptical front propagation and spiral-shaped excitation concentration waves associated with the catalytic oxidation of CO on a Pt(110)-surface was investigated by means of photoemission electron microscopy (PEEM). The properties of these patterns can be tuned through the control parameters, viz., the partial pressures of CO and O2 and the sample temperature. Over a wide range of control parameters the transition between two metastable states (COad and Oad covered surface) proceeds via nucleation and growth of elliptical reaction-diffusion (RD)-fronts. Front velocities and critical radii for nucleation are determined by the diffusion of adsorbed CO under reaction conditions. If at constant pO2, T the CO partial pressure is increased beyond a critical value a transition to qualitatively different dynamic behavior takes place. The elliptical fronts give way to oxygen spiral waves of excitation spreading across the CO-covered areas. For fixed experimental conditions a broad distribution of spatial wavelengths and temporal rotation periods was found. This effect has to be attributed to the existence of surface defects of μm-size to which the spiral tip is pinned. These data lead to a dispersion relation between the front propagation velocity and the wavelength, respectively, period. In addition, the dynamics of free spiral-shaped excitation waves was investigated under the influence of externally modulated temperature. Now the spiral starts to drift, resulting in distortion of the Archimedian shape and a pronounced Doppler effect.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 2128-2148 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The interaction of oxygen with Al(111) was studied by scanning tunneling microscopy (STM). Chemisorbed oxygen and surface oxides can be distinguished in STM images, where for moderate tunnel currents and independent of the bias voltage the former are imaged as depressions, while the latter appear as protrusions. An absolute coverage scale was established by counting O adatoms. The initial sticking coefficient is determined to so=0.005. Upon chemisorption at 300 K the O adlayer is characterized by randomly distributed, immobile, individual O adatoms and, for higher coverages, by small (1×1) O islands which consist of few adatoms only. From the random distribution of the thermalized O adatoms at low coverages a mobile atomic precursor species is concluded to exist, which results from an internal energy transfer during dissociative adsorption. These "hot adatoms'' "fly apart'' by at least 80 A(ring), before their excess energy is dissipated. A model is derived which explains the unusual island nucleation scheme by trapping of the hot adatoms at already thermalized oxygen atoms. Oxidation starts long before saturation of the (1×1) O adlayer, at coverages around aitch-thetaO(approximately-equal-to)0.2. For a wide coverage range bare and Oad covered surfaces coexist with the surface oxide phase. Upon further oxygen uptake both chemisorbed and oxide phase grow in coverage. Oxide nucleation takes place at the interface of Oad islands and bare surface, with a slight preference for nucleation at upper terrace step edges.Further oxide formation progresses by nucleation of additional oxide grains rather than by growth of existing ones, until the surface is filled up with a layer of small oxide particles of about 20 A(ring) in diameter. At very large exposures up to 5×105 L they cover the entire surface as a relatively smooth, amorphous layer of aluminum oxide. The difference in Al atom density between Al metal and surface oxide is accommodated by short range processes, with no indication for any long range Al mass transport. Based on our data we discuss a simpler two step model for the interaction of oxygen with Al(111), without making use of an additional subsurface oxygen species. The complex spectroscopic data for the O/Al(111) system are rationalized by the wide coexistence range of bare and Oad covered surface with surface oxide and by differences in the electronic and vibronic properties of the surface atoms depending on the number of neighboring O adatoms in the small Oad islands.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Catalysis letters 22 (1993), S. 215-225 
    ISSN: 1572-879X
    Keywords: Ion-scattering spectroscopy (ISS) ; methanol oxidation ; oxygen ; Raman spectroscopy ; reflection electron microscopy (REM) ; silver ; X-ray photoelectron spectroscopy (XPS)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Under the applied high reaction temperatures (∼900 K) the Ag surface is restructured and a tightly held oxygen species is formed on the surface (Oγ) apart from O atoms dissolved in the bulk (Oβ). Methanol oxidation to formaldehyde proceeds through this Oγ species as demonstrated by application of a variety of spectroscopic techniques.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 89-98 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The occurrence of instabilities in chemically reacting systems, resulting in unsteady and spatially inhomogeneous reaction rates, is a widespread phenomenon. In this article, we use nonlinear signal processing techniques to extract a simple, but accurate, dynamic model from experimental data of a system with spatiotemporal variations. The approach consists of a combination of two steps. The proper orthogonal decomposition [POD or Karhunen-Loève (KL) expansion] allows us to determine active degrees of freedom (important spatial structures) of the system. Projection onto these “modes” reduces the data to a small number of time series. Processing these time series through an artificial neural network (ANN) results in a low-dimensional, nonlinear dynamic model with almost quantitative predictive capabilities.This approach is demonstrated using spatiotemporal data from CO oxidation on a Pt (110) crystal surface. In this special case, the dynamics of the two-dimensional reaction profile can be successfully described by four modes; the ANN-based model not only correctly predicts the spatiotemporal short-term behavior, but also accurately captures the long-term dynamics (the attractor). While this approach does not substitute for fundamental modeling, it provides a systematic framework for processing experimental data from a wide variety of spatiotemporally varying reaction engineering processes.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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