Advertisement

Sedimentation and diffusion of polyelectrolytes

  • P. M. Budd
Conference paper
Part of the Progress in Colloid & Polymer Science book series (PROGCOLLOID, volume 94)

Abstract

The sedimentation and diffusion behaviour of polyelectrolytes is discussed. The properties of polyelectrolyte solutions are profoundly influenced by intramolecular and intermolecular charge interactions. In the presence of a simple salt, the range of these interactions is reduced, but additional effects arise. For example, the Donnan effect needs to be taken into account in the quantitative analysis of sedimentation data. The Donnan parameter, Γ, may be estimated from the concentration dependence of sedimentation velocity. In the absence of a simple salt, sedimentation coefficients are rather low and diffusion coefficients, at moderate polymer concentrations, are rather high; this has been attributed to coupled motion of polyions and counterions. Results are presented from a synthetic boundary experiment on sodium poly(styrene sulphonate) in salt-free solution which show that the diffusion coefficient depends markedly on polymer concentration below 0.2 g dm−3. This diffusion process appears to be equivalent to the fast diffusion process observed by dynamic light scattering. Current theories of coupled-ion diffusion in salt-free polyelectrolyte solutions are inadequate; the effects of intermolecular interactions and the structure of polyelectrolyte solutions need to be considered.

Key words

Polyelectrolyte sedimentation velocity diffusion analytical ultracentrifuge dynamic light scattering sodium poly(styrene sulphonate) 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Budd PM (1989) In: Allen G, Bevington JC, Booth C, Price C (eds) Comprehensive Polymer Science, Vol 1, Pergamon, Oxford, Chater 10, p 199Google Scholar
  2. 2.
    Budd PM (1989) In: Allen G, Bevington JC, Booth C, Price C (eds) Comprehensive Polymer Science, Vol 1, Pergamon, Oxford, Chapter 11, p 215Google Scholar
  3. 3.
    Budd PM (1992) In: Harding SE, Rowe AJ, Horton JC (eds) Analytical Ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Chapter 32Google Scholar
  4. 4.
    Yamanaka J, Matsuoka H, Kitano H, Ise N (1990) J coll Interf Sci 134:92CrossRefGoogle Scholar
  5. 5.
    Yamanaka J, Matsuoka H, Kitano H, Hasegawa M, Ise N (1990) J Am Chem Soc 112:587CrossRefGoogle Scholar
  6. 6.
    Yamanaka J, Araie H, Matsuoka H, Kitano H, Ise N, Yamaguchi T, Sacki S, Tsubokawa M (1991) Macromolecules 24:3206CrossRefGoogle Scholar
  7. 7.
    Yamanaka J, Araie H, Matsuoka H, Kitano H, Ise N, Yamaguchi T, Saeki S, Tsubokawa M (1991) Macromolecules 24:6156CrossRefGoogle Scholar
  8. 8.
    Ise N (1985) Macromol Chem Suppl 12:215CrossRefGoogle Scholar
  9. 9.
    Donnan FG (1911) Z Elektrochem 17:572Google Scholar
  10. 10.
    Casassa EF, Eisenberg H (1964) Adv Protein Chem 19:287CrossRefGoogle Scholar
  11. 11.
    Eisenberg H (1976) Biophys Chem 5:243CrossRefGoogle Scholar
  12. 12.
    Eisenberg H (1976) Biological Macromolecules and Polyelectrolytes in Solution, Oxford University Press, OxfordGoogle Scholar
  13. 13.
    Budd PM (1988) Brit Polym J 20:33CrossRefGoogle Scholar
  14. 14.
    Budd PM (1985) Polymer 26:1519CrossRefGoogle Scholar
  15. 15.
    Pederson KO (1958) J Phys Chem 62:1282CrossRefGoogle Scholar
  16. 16.
    Mijnlieff PF (1963) In: Williams JW (ed), Ultracentrifugal Analysis, Academic, New York, p. 81Google Scholar
  17. 17.
    Varoqui R, Schmitt A (1972) Biopolymers 11:1119CrossRefGoogle Scholar
  18. 18.
    Alexandrowicz Z, Daniel E (1963) Biopolymers 1:447CrossRefGoogle Scholar
  19. 19.
    Wales M, Van Holde KE (1954) J Polym Sci 14:81CrossRefGoogle Scholar
  20. 20.
    Berne BJ, Pecora R (1976) Dynamic Light Scattering, Wiley, New York, Chapter 9Google Scholar
  21. 21.
    Vink H (1990) J Coll Interf Sci 135:218CrossRefGoogle Scholar
  22. 22.
    Säverborn S (1945) Dissertation, UppsalaGoogle Scholar
  23. 23.
    Nagasawa M, Fujita H (1964) J Am Chem Soc 86:3005CrossRefGoogle Scholar
  24. 24.
    Crank J (1956) The Mathematics of Diffusion, Oxford University Press, OxfordGoogle Scholar
  25. 25.
    Boltzmann L (1894) Ann Physik, Leipzig 53:959CrossRefGoogle Scholar
  26. 26.
    Matano C (1932–33) Jap J Phys. 8:109Google Scholar
  27. 27.
    Mandel M (1993) In: Brown W (ed), Dynamic Light Scattering: The Method and Some Applications, Oxford University Press, Oxford, Chapter 7Google Scholar
  28. 28.
    Lin SC, Lee WI, Schurr JM (1978) Biopolymers 17:1041CrossRefGoogle Scholar
  29. 29.
    Schmitz KS, Lu M, Singh M, Ramsay DJ (1984) Biopolymers 23:1637CrossRefGoogle Scholar
  30. 30.
    Wedlák M (1993) Macromolecules 26:1158CrossRefGoogle Scholar
  31. 31.
    Förster S, Schmidt M, Antonietti M (1990) Polymer 31:781CrossRefGoogle Scholar
  32. 32.
    Drifford M, Dalbiez JP (1985) Biopolymers 24:1501CrossRefGoogle Scholar
  33. 33.
    Sedlák M, Amis EJ (1992) J Chem Phys 96:817CrossRefGoogle Scholar
  34. 34.
    Sedlák M, Amis EJ (1992) J Chem Phys 96:826CrossRefGoogle Scholar
  35. 35.
    Genz U, Benmouna M, Klein R (1991) Macromolecules 24:6413CrossRefGoogle Scholar
  36. 36.
    Li X, Reed WF (1991) J Chem Phys 94:4568CrossRefGoogle Scholar

Copyright information

© Dr. Dietrich Steinkopff Verlag GmbH & Co. KG 1994

Authors and Affiliations

  • P. M. Budd
    • 1
  1. 1.Department of ChemistryUniversity of ManchesterManchesterUK

Personalised recommendations