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Metallurgical Transactions B

, Volume 9, Issue 4, pp 623–629 | Cite as

The Interfacial Kinetics of the Reaction of CO2 with Nickel. Part I: The 14CO2-CO Exchange Reaction and the Influence of Sulfur

  • A. W. Cramb
  • W. R. Graham
  • G. R. Belton
Article

Abstract

The rate of dissociation of CO2 on nickel has been studied by means of the 14CO2-CO exchange reaction. For pure polycrystalline nickel between 500 and 1240°C the forward rate constant, in mole cm−2 s−1 atm−1, is given by:
$$\ln k_f = - 7300/T - 2.57.$$
This is shown to be closely consistent with ideal chemisorption kinetics. Lower apparent rate constants when Ni3S2 is added to the surface or at bulk saturation with sulfur are consistent with a surface blockage mechanism by chemisorbed sulfur which shows a Langmuir adsorption isotherm. The adsorption coefficient of sulfur, in at. pet−1, is deduced to be given by the equation:
$$\ln K_s = 29,100/T - 15.82.$$
Results from associated Auger electron spectroscopic studies are in good accord with an ideal Langmuir adsorption isotherm for sulfur on polycrystalline nickel.

Keywords

Metallurgical Transaction Kcal Mole Apparent Rate Constant Dibutyl Phthalate Peak Height Ratio 
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.

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References

  1. 1.
    A. Ozaki: Isotopic Studies of Heterogeneous Catalysis, Kodansha Ltd., Tokyo and Academic Press, Inc., New York, 1977.Google Scholar
  2. 2.
    H. J. Grabke: Proc. 3rd Int. Congr. Catalysis, pp. 928–38, 1964.Google Scholar
  3. 3.
    H. J. Grabke: Ber. Bunsenges. Phys. Chem., 1967, vol. 71, pp. 1067–73.Google Scholar
  4. 4.
    H. J. Grabke: Ber. Bunsenges. Phys. Chem., 1965, vol. 69, pp. 48–57.Google Scholar
  5. 5.
    H. J. Grabke: Ber. Bunsenges. Phys. Chem., 1966, vol. 70, pp. 664–74.Google Scholar
  6. 6.
    C. Wagner: Advances in Catalysis, vol. 21, pp. 323–81, 1970.CrossRefGoogle Scholar
  7. 7.
    D. R. Sain and G. R. Belton: Met. Trans. B, 1976, vol. 7B, pp. 235–44.CrossRefGoogle Scholar
  8. 8.
    E. T. Turkdogan and J. V. Vintners: Met. Trans., 1972, vol. 3, pp. 1561–74.CrossRefGoogle Scholar
  9. 9.
    M. Byrne: MS Thesis, University of Pennsylvania, 1978.Google Scholar
  10. 10.
    S. C. Brown and W. W. Miller: Rev. Sci. Instr., 1947, vol. 18, pp. 496–500.CrossRefGoogle Scholar
  11. 11.
    H. V. Neher and W. H. Pickering: Phys. Rev., 1938, vol. 53, p. 316.CrossRefGoogle Scholar
  12. 12.
    S. Glasstone, K. J. Laidler, and H. Eyring: The Theory of Rate Processes, McGraw-Hill Book Co., New York, 1941.Google Scholar
  13. 13.
    H. Kersten: Rev. Sci. Instr., 1931, vol. 2, pp. 649–53.CrossRefGoogle Scholar
  14. 14.
    G. A. Meyer: Ph.D. Thesis, Columbia University, 1972.Google Scholar
  15. 15.
    R. J. Brigham, H. Neumeyer, and J. S. Kirkaldy: Can. Met. Quart, 1971, vol. 9, pp. 525–29.CrossRefGoogle Scholar
  16. 16.
    N. Barbouth and J. Oudar: Compt. Rend., 1969, Ser. C.vol. 269, pp. 1618–21.Google Scholar
  17. 17.
    A. C. Yen, W. R. Graham, and G. R. Belton: Met. Trans. A, 1978, vol. 9A, pp. 31–34.CrossRefGoogle Scholar
  18. 18.
    JANAF Thermochemical Tables, 2nd ed., Nat. Stand. Ref. Data Ser., Nat. Bur. Stand., 37, U.S. Govt. Printing Office, Washington, D.C., 1971.Google Scholar
  19. 19.
    J. C. Shelton, H. R. Patil, and J. M. Blakely: Surface Sci., 1974, vol. 43, pp. 493–520.CrossRefGoogle Scholar
  20. 20.
    L. C. Isett and J. M. Blakely: Surface Sci., 1975, vol. 47, pp. 645–49.CrossRefGoogle Scholar
  21. 21.
    L.C. Isett and J. M. Blakely: J. Vac. Sci. Tech., 1975, vol. 12, pp. 237–41.CrossRefGoogle Scholar
  22. 22.
    K. Klier, A. C. Zettlemoyer, and H. Leidheiser: J. Chem. Phys., 1970, vol. 52, pp. 589–602.CrossRefGoogle Scholar
  23. 23.
    G. Wedler, private communication to Ref. [22].Google Scholar

Copyright information

© American Society for Metals and the Metallurgical Society of Aime 1978

Authors and Affiliations

  • A. W. Cramb
    • 1
  • W. R. Graham
    • 1
  • G. R. Belton
    • 1
  1. 1.Department of Metallurgy and Materials ScienceUniversity of PennsylvaniaPhiladelphiaUSA

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