Equilibrium and Non-equilibrium Effects in Adsorption-Desorption Kinetics: Influences of Interaction Dynamics, Reaction Kinetics, and Statistical Mechanics of the Adlayer

  • D. Menzel
Part of the Springer Series in Surface Sciences book series (SSSUR, volume 8)


The various meanings of non-equilibrium in our context (irreversibility of experimental situation; deviation from equilibrium within the layer; non- equilibration in energy and/or momentum transfer during the surface collision, leading to non-equipartition among the various degrees of freedom) are clarified first. If quasi-equi1ibrium persists (no influence of irreversibility; internal equilibrium of the layer), then the expression for desorption rates can be split into an equilibrium factor and a dynamic factor; the latter can be identified with the sticking coefficient and contains the non-equipartition effects. It can then be expected that, depending on circumstances, one or the other will govern the rate behaviour. Examples of experimental results from physisorption as well as chemisorption systems are discussed which show that effects of the statistical mechanics of the adsorbate layer, the internal equilibration of surface layers, and of the microscopic dynamics of the gas-surface interaction can be clearly seen in many cases, even though they can mix and interfere as well. Thermodynamic influences become most obvious if detailed coverage dependences of desorption rate parameters are investigated which can then be used to derive the statistics of the layer. Dynamic effects can be most easily seen in state-resolved beam experiments, but are also obvious in more classical experiments, in particular of sticking coefficients. Some remarks about experimental difficulties are made in an appendix.


Dynamic Effect Detailed Balance Desorption Rate Dissociative Adsorption Transition State Theory 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    J.H. deBoer: The Dynamical Character of Adsorption ( Clarendon Press, Oxford 1968 )Google Scholar
  2. 2.
    See for instance: D. Menzel: In Interactions on Metal Surfaces, ed. by R. Gomer (Springer, Berlin 1975) p.101; D.Ä. King: CRC Crit. Rev. Solid Mater. Sci 7, 167 (1978); J.T. Yates,Jr.: In Solid State Physics: Surfaces, Methods of Experimental Physics, vol. 22, ed. by R.L. Park and M.G. Lagally ( Academic Press, Orlando 1985 ), p. 425Google Scholar
  3. 3.
    D. Menzel: In Chemistry and Physics of Solid Surfaces, ed. by R. Vanselow and R. Howe (Springer Berlin 1982 ), p. 389Google Scholar
  4. 4.
    J.E. Lennard-Jones: Trans. Faraday Soc. 28, 333 (1932)Google Scholar
  5. 5.
    F.O. Goodman, Y. Wachman: Dynamics of Gas-Surface Scattering ( Academic Press, New York 1976 )Google Scholar
  6. 6.
    J.C. Tully: Ann. Rev. Phys. Chem. 31, 319 (1980)Google Scholar
  7. 7.
    H.J. Kreuzer, Z.W. Gortel: Physisorption Kinetics ( Springer, Berlin 1986 ).Google Scholar
  8. 8.
    W. Brenig: this volume, and references therein.Google Scholar
  9. 9.
    J.A. Barker, D.J. Auerbach: Surface Sci. Reports 4, 1 (1985)CrossRefGoogle Scholar
  10. 10.
    G. Comsa, R. David: Surface Sci. Reports 5, 145 (1985)Google Scholar
  11. 11.
    K.D. Rendu!ic, A. Winkler: J. Chem. Phys. 79, 5151 (1983)Google Scholar
  12. 12.
    H.P. Steinrück, M. Luger, A. Winkler, K.D. Rendulic: Phys. Rev. B 32, 5032 (1985); H.P. Steinrück, K.D. Rendulic, A. Winkler, Surface Sci. 152/3, 323 and 154, 99 (1985)CrossRefGoogle Scholar
  13. 13.
    H. Pfnür, P. Feulner, H.A. Engelhardt, D. Menzel: Chem. Phys. Lett., 59, 481 (1978); H. Pfnür, D. Menzel: J. Chem. Phys. 79, 2400 (1983); H. Pfnür, P. Feulner, D. Menzel: J. Chem. Phys. 79, 4613 (1983)Google Scholar
  14. 14.
    W.H. Weinberg: this volume.Google Scholar
  15. 15.
    J.C. Keck: Disc. Faraday Soc. 33, 173 (1962); G. Iche, Ph. Nozieres: J. Physique 37, 1313 (1976); W. Brenig, K. Schönhammer: Z. Physik B24, 91Google Scholar
  16. 16.
    J.C. Tully: Surface Sci. 111, 461 (1981), and this volumeGoogle Scholar
  17. 17.
    S. Glasstone, K.J. Laidler, H. Eyring: The Theory of Rate Processes ( McGraw-Hill, New York 1941 )Google Scholar
  18. 18.
    J. Kouptsidis, D. Menzel: Ber. Bunsenges. Phys. Chem. 74, 512 (1970)Google Scholar
  19. 19.
    W. Brenig: Z. Physik B48, 127 (19.82)Google Scholar
  20. 20.
    M.J. Brei tschafter: Ph.D. Thesis (T.U. München 1985); M.J. Breitschafter, E. Umbach, D. Menzel: in preparationGoogle Scholar
  21. 21.
    H. Sehlichting: Ph.D. Thesis (T.U. München 1987); H. Sehlichting, P. Feulner, D. Menzel: in preparationGoogle Scholar
  22. 22.
    Interestingly, s continues to rise above 1 monolayer and saturates only above 3 monolayers for Ne (fig. 2). This shows that the first 2 layers still feel the influence of weak coupling to the metalGoogle Scholar
  23. 23.
    D. Menzel, J. Kouptsidis: In Gas-Oberflächen-Wechselwirkung ( Dornier, Friedrichshafen 1973 ) p. 282Google Scholar
  24. 24.
    R. Opila, R. Gomer: Surface Sci. 36, 1 (1981)Google Scholar
  25. 25.
    H.J. Kreuzer and D. Menzel, in preparationGoogle Scholar
  26. 26.
    U. Leuthäusser: Z. Phys. B50, 65 (1983)Google Scholar
  27. 27.
    J.E. Hurst, C.A. Becker, J.P. Cowin, K.C. Janda, L. Wharton, D.J. Auerbach: Phys. Rev. Letters 43, 1175 (1979)Google Scholar
  28. 28.
    H. Pfnür, D. Menzel: Surface Sci. 148, 411 (1984)Google Scholar
  29. 29.
    G. Michalk, W. Moritz, H. Pfnür, D. Menzel: Surface Sci. 129, 92 (1983)Google Scholar
  30. 30.
    E.D. Williams, W.H. Weinberg: Surface Sci. 82, 93 (1979); H. PfnLir, H. J. Heier: Ber. Bunsenges. phys. chem. 90, 272 (1986)Google Scholar
  31. 31.
    H. Pfnür, D. Menzel, F.M. Hoffmann, A. Ortega, A.M. Bradshaw: Surface Sci. 93, 431 (1980)Google Scholar
  32. 32.
    U. Leuthäusser: Z. Physik B37, 65 (1980)Google Scholar
  33. 33.
    D. Menzel, H. Pfnür, P. Feulner: Surface Sci. 126, 374 (1983)Google Scholar
  34. 34.
    H. Ibach, W. Erley, H. Wagner: Surface Sci. 92, 28 (1980)Google Scholar
  35. 35.
    D. Menzel: In Proceedings of the 3S’83 Conference Obertraun, ed. by P. Braun et al. (HTU Wien 1983 ) p. 218Google Scholar
  36. 36.
    J. Segner, H. Robota, W. Vielhaber, G. Ertl, F. Frenke!, J. Häger, W. Krieger, H. Walter: Surface Sci. 131, 273 (1983)Google Scholar
  37. 37.
    R.R. Cavanagh, D.S. King: Phys. Rev. Letters 46, 1829 (1981)Google Scholar
  38. 38.
    D.O. Hayward, A.O. Taylor: Chem. Phys. Letters 124, 264 (1986)Google Scholar
  39. 39.
    G. Cornsa, R. David, B. J. Schumacher: Surface Sci. 85, 45 (1979)Google Scholar
  40. 40.
    H.P. Steinrück: private communicationGoogle Scholar
  41. 41.
    S. Andersson, J. Harris: Phys. Rev. B27, 9 (1983); S. Andersson, L. Wilzen, J. Harris: Phys. Rev. Letters 55, 2591 (1985)CrossRefGoogle Scholar
  42. 42.
    K. Christmann, F. Chehab, V. Penka, G. Ertl: Surface Sci. 152/53, 356 (1985)Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1987

Authors and Affiliations

  • D. Menzel
    • 1
  1. 1.Physik-DepartmentTechnische Unversität MünchenGarchingFed. Rep. of Germany

Personalised recommendations