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  • 1
    Digitale Medien
    Digitale Medien
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 95 (1991), S. 1294-1299 
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 307-319 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The periodically perturbed oscillations in the isothermal CO oxidation on a Pt(110) surface at low pressure were modeled using the recently developed reconstruction model of kinetic oscillations, in which the usual Langmuir–Hinshelwood mechanism is coupled with the CO-driven 1×2(arrow-right-and-left)1×1 phase transition of the surface. The experimental findings (entrainment bands, quasiperiodicity, critical slowing down) could be well reproduced with this model. The calculations revealed a complicated bifurcation fine structure of the Arnol'd tongues. While the skeleton structure turned out to be the same as in other studies, some additional features were found, and several details (mainly in the p/2 tongues) were different from forced systems examined previously. A co-dimension-3 bifurcation (in which a second-order resonance coincides with a degenerate period doubling) is discussed in this context.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 9161-9172 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The parameters entering the kinetics for the mechanism of catalytic CO oxidation have been adapted for a Pt(110) surface, giving rise to a two-variable model correctly predicting bistability. Oscillations are obtained when, in addition, the adsorbate-driven 1×2–1×1 structural phase transition of Pt(110) is taken into account. Mixed-mode oscillations can be qualitatively explained by including the faceting of the surface as a fourth variable. The limitations of the model essentially stem from the fact that only ordinary differential equations have been analyzed so far neglecting spatial pattern formation. It is discussed which dynamic phenomena observed experimentally in the CO oxidation on Pt(110) will probably not be adequately describable without taking spatial effects into account.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 510-521 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The rate of catalytic CO oxidation on Pt(100) and (110) surfaces at low pressures (≤10−4 Torr) and under isothermal conditions may exhibit sustained temporal oscillations which are coupled with periodic transformations of the surface structures between reconstructed and nonreconstructed phases, the latter exhibiting higher oxygen sticking coefficients and hence higher reactivity. With Pt(100) the two surface phases exhibit a much larger difference in reactivity (=oxygen sticking coefficient) than with Pt(110), which effect accounts for the qualitative differences in the oscillatory behavior: if two of the control parameters (say pO2, T) are kept fixed, the third (pCO) may be varied with Pt(100) over a fairly wide range without leaving the oscillatory region. Minor (〈1%) fluctuations of the partial pressures associated with the varying reaction rate are hence without any noticeable effect. Coupling between surface reaction and diffusion causes wave propagation of the surface phase transformations and therefore spatial self-organization, as demonstrated by scanning LEED experiments. With Pt(110), on the other hand, the oscillatory region is very narrow. In this case mass transport through the gas phase as caused by the small pressure variations associated with the reaction lead to synchronization between different parts of the surface. Computer simulations with the cellular automaton technique confirm qualitatively the experimental findings and support the conclusions reached.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 8595-8604 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A two-variable Langmuir–Hinshelwood mechanism for isothermal CO oxidation on a catalytically active surface is presented. It shows bistability stemming from 2 cusp bifurcations, which can be obtained analytically for low pressure. Inclusion of CO diffusion on the surface leads to a system of partial differential equations, which exhibits nucleation and front propagation phenomena in the bistable region. While the line of equistability could with good accuracy be solved for analytically, the front velocities and critical radii for nucleation had to be determined numerically (using the method of heteroclinic orbits). Throughout the calculations the kinetics and rate constants for the CO oxidation on Pt(111) are used. Here the model can be reduced by adiabatic elimination of one variable (namely oxygen coverage) allowing a comparison to the exactly solved one-variable Schlögl model. Possible implications for future experimental work are briefly discussed.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 4555-4563 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A dynamic model designed to describe bistability and kinetic oscillations of the reaction rate during the oxidation of CO on a Pt(110) single crystal surface is extended by incorporating surface diffusion of adsorbed CO in order to analyze the properties of traveling waves propagating on the catalytically active surface. In the range of control parameters (partial pressure of oxygen and carbon monoxide and temperature) which corresponds to excitable dynamics, solitary pulses and periodic wave trains can be triggered. Using both asymptotic and numerical methods, the velocity and shape of the pulses as well as the dispersion relation for periodic wave trains are determined and compared to experimental data where available.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    Woodbury, NY : American Institute of Physics (AIP)
    Chaos 4 (1994), S. 499-508 
    ISSN: 1089-7682
    Quelle: AIP Digital Archive
    Thema: Physik
    Notizen: Among heterogeneously catalyzed chemical reactions, the CO oxidation on the Pt(110) surface under vacuum conditions offers probably the greatest wealth of spontaneous formation of spatial patterns. Spirals, fronts, and solitary pulses were detected at low surface temperatures (T〈500 K), in line with the standard phenomenology of bistable, excitable, and oscillatory reaction-diffusion systems. At high temperatures (T(approximately-greater-than)540 K), more surprising features like chemical turbulence and standing waves appeared in the experiments. Herein, we study a realistic reaction-diffusion model of this system, with respect to the latter phenomena. In particular, we deal both with the influence of global coupling through the gas phase on the oscillatory reaction and the possibility of wave instabilities under excitable conditions. Gas-phase coupling is shown to either synchronize the oscillations or to yield turbulence and standing structures. The latter findings are closely related to clustering in networks of coupled oscillators and indicate a dominance of the global gas-phase coupling over local coupling via surface diffusion. In the excitable regime wave instabilities in one and two dimensions have been discovered. In one dimension, pulses become unstable due to a vanishing of the refractory zone. In two dimensions, turbulence can also emerge due to spiral breakup, which results from a violation of the dispersion relation.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Woodbury, NY : American Institute of Physics (AIP)
    Chaos 12 (2002), S. 215-230 
    ISSN: 1089-7682
    Quelle: AIP Digital Archive
    Thema: Physik
    Notizen: The spatial coupling in electrochemical systems is mediated by ion migration under the influence of the electric field. Since field effects spread very rapidly, every point of an electrode can communicate with every other one practically instantaneously through migration coupling. Based on mathematical potential theory we present the derivation of a generally applicable reaction–migration equation, which describes the coupling via an integral over the whole electrode area. The corresponding coupling function depends only on the geometry of the electrode setup and has been computed for commonly used electrode shapes (such as ring, disk, ribbon or rectangle). The pattern formation observed in electrochemical systems in the bistable, excitable and oscillatory regime can be reproduced in computer simulations, and the types of patterns occurring under different geometries can be rationalized. © 2002 American Institute of Physics.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 1202-1214 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A systematic study of spiral waves in a realistic reaction-diffusion model describing the isothermal CO oxidation on Pt(110) is carried out. Spirals exist under oscillatory, excitable, and bistable (doubly metastable) conditions. In the excitable region, two separate meandering transitions occur, both when the time scales become strongly different and when they become comparable. By the assumption of surface defects of the order of 10 μm, to which the spirals can be pinned, the continuous distribution of wavelengths observed experimentally can be explained. An external periodic perturbation generally causes a meandering motion of a free spiral, while a straight drift results, if the period of the perturbation divided by the rotation period is a natural number.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 7613-7618 
    Quelle: ACS Legacy Archives
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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