Exclusion Chromatography—Mechanism and Materials

  • S. G. Perry
  • R. Amos
  • P. I. Brewer


Exclusion chromatography is a branch of liquid chromatography in which a solute is distributed between the free solvent and the solvent contained in the interstices of porous particles. The free solvent is the mobile phase and the porous particles containing the solvent constitute the stationary phase (the porous particles themselves are often loosely referred to as the stationary phase). The separation depends upon the fact that the interstices are of such a size that the degree of penetration of the solute molecules depends upon the size of these molecules. Very large molecules are unable to enter the stationary phase and are eluted in a volume of solvent equal to the void volume of the column, i.e., the volume of the free solvent in the column. If the solute molecules are sufficiently small so that they can penetrate into the whole of the solvent contained in the stationary phase, they are eluted by a volume of solvent equal to the void volume of the column plus the volume of solvent contained in the stationary phase, i.e., equal to the total volume of solvent in the column. Thus, providing adsorption effects are absent, exclusion chromatography separates according to size, large molecules being eluted before small molecules. All solutes are eluted in the comparatively narrow range of eluent volumes between the void volume of the column and the total volume of the solvent in the column.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Giddings, J. C., Anal. Chem. 39, 1027 (1967).CrossRefGoogle Scholar
  2. 2.
    Moore, J. C. J. Polymer Sci. A-22, 835 (1964).Google Scholar
  3. 3.
    Yau, W. W., Malone, C. P., and Suchan, H. L., Preprints, Division of Petroleum Chemistry, Am. Chern. Soc., 15, A63 (1970).Google Scholar
  4. 4.
    Ginsberg, B. Z., and Cohen, D., Trans. Faraday Soc., 60, 185 (1964).CrossRefGoogle Scholar
  5. 5.
    Porath, J., Pure Appl. Chem. 6, 233 (1963).CrossRefGoogle Scholar
  6. 6.
    Laurent, T. C., and Killander, J., J. Chromatog. 14, 317 (1964)CrossRefGoogle Scholar
  7. 7.
    Ogston, A. G., Trans. Faraday Soc. 54, 1754 (1958).CrossRefGoogle Scholar
  8. 8.
    Moore, J. C., and Arrington, M. C., Preprints, Third International Seminar on Gel Permeation Chromatography, Geneva (1966).Google Scholar
  9. 9.
    {paDe} Vries, A. J., {paLe} Page, M., Beau, R., and Guillemin, C. L., Anal. Chem. 39, 935 (1968).Google Scholar
  10. 10.
    Casassa, E. F., Polymer Letters 5, 773 (1967).CrossRefGoogle Scholar
  11. 11.
    Giddings J. C., Kucera, E., Russell, C. P., and Myers, M. N., J. Phys. Chem. 72, 4397 (1968).CrossRefGoogle Scholar
  12. 12.
    Casassa, E. F., and Tagami, Y., Macromolecules 2, 14 (1969).CrossRefGoogle Scholar
  13. 13.
    Kwok, J., and Snyder, L. R., Anal. Chem. 40, 118 (1968).CrossRefGoogle Scholar
  14. 14.
    Haller, W. J., J. Chem. Phys. 42, 686 (1965).CrossRefGoogle Scholar
  15. 15.
    Haller, W. J., Nature 206, 693 (1965).CrossRefGoogle Scholar
  16. 16.
    {paDe} Vries, A. J., {paLe} Page, M., and Beau, R., J. Polymer Sci. C 21, 119 (1968).Google Scholar
  17. 17.
    Kelley, R. N., and Billmeyer, Jr., F. W., Preprints, Division of Petroleum Chemistry Am. Chem. Soc. 15, A157 (1970).Google Scholar
  18. 18.
    Cooper, A. R., Cain, J. H., Barrall, E. M., and Johnson, J. F., Preprints, Division of Petroleum Chemistry, Am. Chern. Soc. 15, A95 (1970).Google Scholar
  19. 19.
    Heitz, W., Klatyk, K., Kraffczyk, F., Pfitzner, K., and Randau, D., in Proc. Seventh International Seminar on GPC, Monte Carlo, p. 214 (1969).Google Scholar
  20. 20.
    Mair, B. J., Hwang, P. T. R., and Ruberto, R. G., Anal. Chem. 39, 838 (1967).CrossRefGoogle Scholar
  21. 21.
    Green, J. H. S., and Vaughan, M. F., Chem. Ind. 829 (1958).Google Scholar
  22. 22.
    Meyerhoff, G., J. Polymer Sci. C 21, 31 (1958).CrossRefGoogle Scholar
  23. 23.
    Brandrup, J., and Immergut, E. H., (eds.), Polymer Handbook, Interscience Publishers, New York (1966).Google Scholar
  24. 24.
    Benoit, H., Rempp, P., and Grubisic, Z., Polymer Letters 5, 753 (1967).CrossRefGoogle Scholar
  25. 25.
    Coll, H., and Gilding, D. K., J. Polymer Sci. A-2 8, 89 (1970).CrossRefGoogle Scholar
  26. 26.
    Hendrickson, J. G., Anal. Chem. 40, 49 (1968).CrossRefGoogle Scholar
  27. 27.
    Harmon, D. J., J. Polymer Sci. C, 8, 243 (1965).CrossRefGoogle Scholar
  28. 28.
    Duerksen, J. H., Preprints, Division of Petroleum Chemistry, Am. Chern. Soc. 15, A47 (1970).Google Scholar
  29. 29.
    Alliet, D., J. Polymer Sci. A-1 5, 1783 (1967).CrossRefGoogle Scholar

Further Reading

  1. Determann, H., Gel Chromatography, Springer-Verlag, Berlin (1968). (Deals with the theory and practice of exclusion chromatography in both aqueous and nonaqueous solutions.)Google Scholar
  2. Cazes, J., J. Chem. Ed. 47, A461, A505 (1970). (A good account of the practice of exclusion chromatography in nonaqueous solutions.)Google Scholar
  3. Altgelt, K. H., Advan. Chromatog. 7, 3–46 (1968). (A review of the theory of exclusion chromatography, now rather dated.)Google Scholar
  4. Peaker, F. W., in Chromatography, Browning, D. R., ed., McGraw-Hill, London (1969). (A concise article on exclusion chromatography in nonaqueous solution.)Google Scholar

Copyright information

© Springer Science+Business Media New York 1973

Authors and Affiliations

  • S. G. Perry
    • 1
  • R. Amos
    • 1
  • P. I. Brewer
    • 1
  1. 1.Esso Petroleum CompanyLimited Esso Research Centre AbingdonBerkshireEngland

Personalised recommendations