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Ligand-Metal Surface Interactions: Synthesis, Structure and Reactivity

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Metal-Ligand Interactions

Part of the book series: NATO ASI Series ((ASIC,volume 474))

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Abstract

Surface chemistry under high pressure of gaseous reactants is often different from surface chemistry at low pressure. For example, many surface chemical reactions proceed readily under high pressure conditions typical of a commercial, heterogeneous catalytic reaction but appear not to proceed at low pressures(<10-4 torr), despite favorable thermodynamics. The different chemistry and, in particular, the lack of reactivity at the low pressures where ultrahigh vacuum surface science techniques are operable is known loosely as the pressure gap and casts doubt on the relevance of UHV surface chemistry to high pressure processes such as catalysis, chemical vapor deposition and etching reactions. One proposal for the origin of this pressure gap in the catalytic reactivity was the presence of a barrier to the dissociative chemisorption of at least one of the reactants [1,2]. Since it is the translational energy of the incident molecule that is important in sunnounting this barrier and not the surface temperature, the rate of the reaction is limited by the flux of incident molecules with energies above the energy of the barrier. High pressures simply increase the absolute number (not the fraction) of high energy molecules, thereby increasing the reaction rate sufficiently for the products to be detected. This hypothesis was verified by the demonstration of the translational activation of C14 on Ni(111) and the ensuing favorable comparison between the rate constants for C14 dissociation calculated from the low pressure dissociation probability measurements and the rates as measured under high pressure conditions [3-5]. The agreement between the low and high pressure experiments carried out in different laboratories formly establishes

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Authors and Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, 02139, Cambridge, MA, USA

    S. T. Ceyer

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Editors and Affiliations

  1. Dipartimento di Chimica, Università della Calabria, Arcavacata di Rende, I-87030, Cosenza, Italy

    Nino Russo

  2. Département de Chimie, Université de Montréal, C.P. 6128 Succ. A, Montréal, H3C 3J7, Québec, Canada

    Dennis R. Salahub

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© 1996 Kluwer Academic Publishers

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Ceyer, S.T. (1996). Ligand-Metal Surface Interactions: Synthesis, Structure and Reactivity. In: Russo, N., Salahub, D.R. (eds) Metal-Ligand Interactions. NATO ASI Series, vol 474. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0155-1_5

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  • DOI: https://doi.org/10.1007/978-94-009-0155-1_5

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-94-010-6556-6

  • Online ISBN: 978-94-009-0155-1

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