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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 11551-11573 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The catalytic oxidation of CO by oxygen on a platinum (111) single-crystal surface in a gas-flow reactor follows the Langmuir–Hinshelwood reaction mechanism. It exhibits two macroscopic stable steady states (low reactivity: CO-covered surface; high reactivity: O-covered surface), as determined by mass spectrometry. Unlike other Pt and Pd surface orientations no temporal and spatiotemporal oscillations are formed. Accordingly, CO+O/Pt(111) can be considered as one of the least complicated heterogeneous reaction systems. We measured both the macroscopic and mesoscopic reaction behavior by mass spectrometry and photoelectron emission microscopy (PEEM), respectively, and explored especially the region of the phase transition between low and high reactivity. We followed the rate-dependent width of an observed hysteresis in the reactivity and the kinetics of nucleation and growth of individual oxygen and CO islands using the PEEM technique. We were able to adjust conditions of the external control parameters which totally inhibited the motion of the reaction/diffusion front. By systematic variation of these conditions we could pinpoint a whole region of external control parameters in which the reaction/diffusion front does not move. Parallel model calculations suggest that the front is actually pinned by surface defects. In summary, our experiments and simulation reveal the existence of an "experimental" bistable region inside the "computed" bistable region of the reactivity diagram (S-shaped curve) leading to a novel dollar ($)-shaped curve. © 1999 American Institute of Physics.
    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 106 (1997), S. 4291-4308 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The reactive behavior of catalytic CO oxidation on Pt(210) is studied by means of combined reaction rate measurements and photoelectron emission microscopy (PEEM). These methods allow an investigation of the phenomena at macroscopic and mesoscopic level, respectively. The external control parameters (flow rate, CO and oxygen partial pressures, surface temperature and scanning rates of pressure and temperature) are systematically varied to reveal various reactive regions in parameter space. The macroscopic measurements for a given temperature and flow rate (under isothermal conditions) show that lower pressures lead to a pronounced clockwise hysteresis in the production rate of CO2, while increasing pressures cause a systematic narrowing leading to a crossing of the two hysteresis branches into a region of counterclockwise hysteresis. A further pressure increase leads to macroscopic temporal oscillations. Mesoscopic spatiotemporal oscillations appear at the same conditions. The resulting macroscopic isothermal kinetic phase diagram exhibits a cross-shaped characteristic similar to that previously obtained for the Pd(110) surface. The mesoscopic lateral distribution of CO and oxygen adsorbed on the surface is monitored with the photoelectron emission microscope during the reaction at isothermal conditions and different constant oxygen pressures. The observed mesoscopic spatiotemporal patterns, such as islands, waves, target patterns and spirals, are correlated via the external control parameters with different regions in the macroscopic isothermal phase diagram. The results are compared with previous data of CO oxidation on other surfaces, like Pd(110) and Pt(110). © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1543-1549 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Special kinetic behaviors in isothermal reactions on heterogeneous catalysts composed of two components with different roles are studied with the focus on hi stabilities that could occur in stirred-tank flow reactors when control of catalytic sites on one component by mobile (spillover) species produced by the other operates. The comprehensive kinetic model involves: (1) generation of spillover species on the second phase, their transfer to the potentially catalytic phase, and their reaction with this acceptor to generate selective sites; (2) the kinetics of the catalytic reaction. We developed a model for selective catalytic oxidation, where catalyst sites change from nonselective to selective under the influence of the control by spillover oxygen. The model is based on the system of differential equations. By integration and iteration to the steady state for each value of the external control parameter under investigation, the oxygen and hydrocarbon reactant consumption, as well as the state of the catalyst, is calculated. These calculations predict bistable selectivity for certain ranges of concentration in the feed. Data on the boundaries of the hysteresis loops as a function of catalyst composition and oxygen partial pressure are discussed, as well as the variation of these hysteresis boundaries as a function of the internal parameters.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 6 (1955), S. 397-410 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: On the Selection of Contact Agent MaterialThe present state of developement of the heterogeneous catalysis is displayed at hand of the latest literature. Special consideration is paid to the relations of the catalytic activity and the structure of catalysis. Contact-potential and electric conductivity and chemisorption measurements as well as the determination of the coefficient of accomodation have been proved good for the research of contact surface process. The Taylor theory of active centres and the balandin “Multiplett” theory and the Schwab “Adlineation” theory are compared with the modern conception of a frequently decicive influence of the electron configuration of a catalyst. The discussion results in new points of view even for the selection of contact agents of industrially important reactions.
    Notes: Anhand der neueren Literatur wird der gegenwärtige Entwicklungsstand auf dem Gebiet der heterogenen Katalyse beschrieben, wobei die Zusammenhänge zwischen der katalytischen Aktivität und der Struktur des katalysators besonders berücksichtigt werden. Als Untersuchungsmethoden für die Vorgänge in der Katalysatoroberfläche haben sich Kontaktpotential-, elektrische Leitfähigkeits- und Chemisorptionsmessungen und die Bestimmung des Akkommodationskoeffizienten besonders bewährt. Die TAYLOR- sche Theorie der „aktiven Zentren“, die Balandinsche „Multiplett-Theorie“ und die Schwabsche „Adlineations-Theorie“ werden der heutigen Auffassung eines vielfach maßgebenden Einflusses der Elektronenkonfiguration eines katalysators gegenübergestellt. Dabei ergeben sich auch für die Auswahl von Kontaktkatalysatoren technisch wichtiger Reaktionen neue Gesichtspunkte.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 7 (1956), S. 127-137 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Material Secting Viewpoints for Contact Catalysts. Part II. Behavior and Properties of semiconducting CatalystsCondensed from the late literature non metal contact agents of the heterogenous catalysis are reviewed with respect to their semiconducting properties. By means of numerous works of different sources a causality between catalytic activity and electronic disturbances could be proved. In the discussion of some special types of reaction-decomposition of N2O, H2O2, O3, oxidation of CO, SO2, NH3, numerous reactions of hydrogenation, dehydrogenation, dehydration and some rearrangements and cleavages of organic molecules-two general kinds of reaction were created. Donator reactions forming kations of the reactants at a measurable rate on the surface of the contact during the course of reaction, are catalysed well by p-conducting agents. Acceptor reactions, characterized by a formation of anions in the velocity terminating intermediate reactions, are catalysed favorably by n-conductors.Electronic disturbances will always be ineffective if an innermolecular rearrangement, proceeding without any electron transition to or from the contact, becomes termitating velocity of reaction. By means of the semiconducting properties many causalities between the catalytic activity and the material properties of the contacts can be deduced for numerous contacts and reactions. The causalities, however, are of qualitative character and limited validity as the essential factors for catalytic reactions can only be demonstrated exactly with regard to the surface bonds of the activated complex (intermediate state).
    Notes: Nichtmetallische Kontaktmassen der heterogenen Katalyse werden vom Blickwinkel ihrer Halbleitereigenschaften aus in Form einer Zusammenfassung neuerer Literatur betrachtet. An Hand zahlreicher Arbeiten aus verschiedensten Quellen kann gezeigt werden, daß zwischen der katalytischen Wirksamkeit und der elektronischen Fehlordnung der Kontakte kausale Zusammenhänge bestehen. Bei der Besprechung einzelner Reaktionstypen - des N2O-Zerfalls, der CO-Oxydation, des H2O2-Zerfalls, des Ozonzerfalls, der SO2-Oxydation der NH3-Oxydation, zahlreicher Hydrierungs-, Dehydrierungs- und Dehydratisierungsreaktionen und einiger Umlagerung- und Spaltreaktionen organischer Molekeln-wird zwischen zwei Reaktionsarten unterschieden. DONATOR-Reaktionen, die während des Reaktions-Ablaufs mit meßbarer Geschwindigkeit Kationen der Reaktanten an der Katalysatoroberfläche ausbilden, werden durch p-leitende Katalysatoren gut katalysiert. AKZEPTOR-Reaktionen, gekennzeichnet durch eine Anionenausbildung im geschwindigkeitsbestimmenden Teilschritt der Reaktion, werden durch n-Leiter bevorzugt katalysiert.Ohne Einfluß ist die Fehlordnung immer dann, wenn Umlagerungen innerhalb der Molekeln, die ohne einen Elektronenübergang zum (oder vom) Katalysator verlaufen, geschwindigkeitsbestimmend werden.Mit Hilfe der Halbleitereigenschaften lassen sich für zahlreiche Kontakte und Reaktionen Zusammenhänge zwischen katalytischer Wirksamkeit und den Stoffeigenschaften des Kontaktes herleiten. Diese Zusammenhänge tragen jedoch nur qualitativen Charakter und sind nur beschränkt gültig, da die für die katalytische Reaktion wesentlichen Faktoren nur durch die Oberflächenbindung des aktivierten Komplexes (Zwischenzustandes) streng dargestellt werden können.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemie Ingenieur Technik - CIT 56 (1984), S. 610-611 
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemie Ingenieur Technik - CIT 63 (1991), S. 615-618 
    ISSN: 0009-286X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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