Skip to main content
SpringerLink
Log in

Relationship between retention behavior and molecular structure in HPLC. Correlation between solubility parameter and molecular properties

  • Originals
  • Published:
Chromatographia Aims and scope Submit manuscript

Summary

The application and significance of the solubility parameter are detailed for chromatographic systems. A critical review of the general concept and several empirical and semi-empirical equations for the solubility parameter are reported. Using the basic theory and a systematic study of the main factors affecting total (or expanded) solubility parameters (δT) along with boiling points and molar volumes, we found correlations between four kinds of solubility parameter obtained by different methods, which unify their calculation and establish an equation for the calculation of δT, successfully applying it to retention prediction in GC and LC. The results show our approach is more accurate and simplifies to a two-parameter model involving fundamental physicol-chemical parameters. In addition, the variation of δT with the carbon number of homologous series was investigated, mathematical models were derived by multi-regression analysis.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

Abbreviations

Cn :

number of carbon atoms

E:

molar cohesive energy (cal·mol−1)

ΔH gl :

molar vaporization enthalpy (cal·mol−1)

R:

gas constant (1.987 cal·mol−1·K−1)

T:

absolute temperature (K)

Tb :

boiling point temperature (K)

ΔU gl :

molar vaporization energy (cal·mol−1)

V:

molar volume (cm3·mol−1

π:

solubility parameter (cal1/2·cm−3/2)

δHa :

Hansen's solubility parameter (cal1/2·cm−3/2)

δHi :

Hildebrand's solubility parameter (cal1/2·cm−3/2)

δHo :

Hoy's solubility parameter (cal1/2·cm−3/2)

δT, δt :

total solubility parameter (cal1/2·cm−3/2)

g:

gas

k:

variable

a:

acid

b:

boiling point or base

di:

dispersion

g:

gas

hb:

hydrogen bonding

ii:

adjacent i molecules

in:

induction

k:

variable

l:

liquid

n:

number

or:

orientation

p:

polar

t, T:

total

References

  1. Zhang Hongwei, Hu Zhide, Chromatographia33, 575 (1992).

    Article  Google Scholar 

  2. N. Chen, Y. Zhang, P. Lu, J. Chromatogr.606, 1 (1992).

    Article  Google Scholar 

  3. F. M. Yamamoto, S. Rokushika, J. Chromatogr.515, 3 (1990).

    Article  Google Scholar 

  4. P. L. Smith, W. T. Cooper, Chromatographia25, 55 (1988).

    Google Scholar 

  5. F. M. Yamamoto, S. Rokushika, H. Hatano, J. Chromatogr.408, 21 (1987).

    Google Scholar 

  6. H. A. Cooper, R. J. Hurtubise, J. Chromatogr.360, 327 (1986).

    Article  Google Scholar 

  7. T. L. Hafkenscheid, E. Tomlinson, J. Chromatogr.264, 47 (1983).

    Article  Google Scholar 

  8. H. A. H. Billiet, P. J. Schoenmakers, L. D. Galan, J. Chromatogr.218, 443 (1981).

    Article  Google Scholar 

  9. P. J. Schoenmakers, H. A. H. Billiet, L. D. Galan, J. Chromatogr.218, 261 (1981).

    Article  Google Scholar 

  10. P. J. Schoenmakers, H. A. H. Billiet, R. Tijssen, L. D. Galan, J. Chromatogr.149, 519 (1978).

    Article  Google Scholar 

  11. B. L. Karger, L. R. Snyder, C. Eon, J. Chromatogr.125, 71 (1976).

    Article  Google Scholar 

  12. R. Tijssen, H. A. H. Billiet, P. J. Schoenmakers, J. Chromatogr.122, 185 (1976).

    Article  Google Scholar 

  13. H. Burrell, Polymer Handbook, 2nd ed., J. Brandrup, E. H. Immergut, Eds, John Wiley & Sons Interscience, New York, 1975, IV-337.

    Google Scholar 

  14. D. W. V. Krevelen, Properties of Polymers, Elsevier Scientific Publishing Co., Amsterdam, 1976, p. 129.

    Google Scholar 

  15. R. A. Keller, L. R. Snyder, J. Chromatogr. Sci.9, 346 (1971).

    Google Scholar 

  16. B. L. Karger, L. R. Snyder, C. Eon, Anal. Chem.50, 2126 (1978).

    Article  Google Scholar 

  17. K. Sreenivasan, J. Liquid Chromatogr.13, 383 (1990).

    Google Scholar 

  18. J. H. Hildebrand, R. L. Scott, Regular Solutions, Prentice-Hall, Englewood Cliffs, N. J., 1962.

    Google Scholar 

  19. J. H. Hildebrand, J. M. Prausnitz, R. L. Scott, Regular and Related Solution, Van Nostrand-Reinhold, Princeton, N. J., 1970.

    Google Scholar 

  20. J. H. Hildebrand, R. L. Scott, Solubility of Non-Electrolytes, 3rd ed., Reinhold, New York, 1950; Dover, New York, 1964.

    Google Scholar 

  21. K. L. Hoy, J. Paint Technol.42, 76 (1970).

    Google Scholar 

  22. H. Burrell, Interchem. Rev.14, 3 (1955);14, 31 (1955).

    Google Scholar 

  23. H. Burrell, Off. Dig. Fed. Paint Varn. Prod. Clubs,27, 726 (1955).

    Google Scholar 

  24. R. A. Keller, B. L. Karger, L. R. Snyder, in: R. Stock (Editor), Gas Chromatography 1970, Institute of Petroleum, London, 1971, p. 125.

    Google Scholar 

  25. B. L. Karger, L. R. Snyder, C. Horvath, An Introduction to Separation, John Wiley & Sons, New York, 1973.

    Google Scholar 

  26. L. R. Snyder, Separation and Purification, 3rd ed., E. S. Perry, A. Weissberger, Eds., John Wiley & Sons-Interscience, New York, 1978, p. 25.

    Google Scholar 

  27. A. F. M. Barton, Chem. Rev.75, 731 (1975).

    Article  Google Scholar 

  28. C. M. Hansen, A. Beerbower, in: H. F. Mark, J. J. McKetta, D. F. Othmer (Editors), Kirk-Othmer Encyclopedia of Chemical Technology, Suppl. Vol., New York, 2nd ed., 1971, p. 889.

  29. E. B. Bagley, T. P. Nelson, J. M. Scigliano, J. Phys. Chem.77, 2794 (1973); J. Paint Technol.43, 35 (1971).

    Article  Google Scholar 

  30. E. B. Bagley, J. M. Scigliano, Polym. Eng. Sci.11, 177 (1971).

    Article  Google Scholar 

  31. E. B. Bagley, J. P. Nelson, J. W. Barlow, S. A. Chen, Ind. Eng. Chem. Fundam.10, 27 (1971);9, 93 (1970).

    Article  Google Scholar 

  32. I. A. Wielle, E. B. Bagley, A. I. Ch. E. J.13, 836 (1967).

    Google Scholar 

  33. C. M. Hansen, J. Paint Technol.39, 104 (1967).

    Google Scholar 

  34. C. M. Hansen, J. Paint Technol.39, 505 (1967).

    Google Scholar 

  35. C. M. Hansen, Skand. Tidskr. Faerg. Lack13, 132 (1967) (English).

    Google Scholar 

  36. C. M. Hansen, Skand. Tidskr. Faerg. Lack14, 14 (1968);14, 23 (1968) (English).

    Google Scholar 

  37. C. M. Hansen, Ind. Eng. Chem. Prod. Rev. Dev.8, 2 (1969).

    Article  Google Scholar 

  38. C. M. Hansen, J. Paint Technol.42, 660 (1970).

    Google Scholar 

  39. C. M. Hansen, Skand. Tidskr. Faerg. Lack17, 69 (1971) (English).

    Google Scholar 

  40. C. M. Hansen, J. Paint Technol.44, 57 (1972).

    Google Scholar 

  41. C. M. Hansen, Chem. Technol.2, 547 (1972).

    Google Scholar 

  42. C. M. Hansen, Ind. Eng. Chem. Prod. Res. Dev.16, 266 (1977).

    Article  Google Scholar 

  43. C. M. Hansen, Farbe Lack83, 595 (1977 (German).

    Google Scholar 

  44. C. M. Hansen, P. E. Pierce, Ind. Eng. Chem. Prod. Res. Dev.13, 218 (1974).

    Article  Google Scholar 

  45. C. M. Hansen, K. Skaarup, J. Paint Technol.39, 511 (1967).

    Google Scholar 

  46. K. L. Hoy, Tables of Solubility Parameter, Union Carbide Corp., South Charleston, W. Va., 1969.

    Google Scholar 

  47. K. L. Hoy, Tables of Solubility Parameter, 3rd ed., Union Carbide Corporation, Chemical and Plastics Research and Development Dept., South Charleston, W. Va., 1975.

    Google Scholar 

  48. H. Burrell, Adv. Chem. Ser.124, 1 (1973).

    Google Scholar 

  49. Z. L. Sun, M. C. Liu, Z. D. Hu, Proc. 2nd Beijing Conf. and Exhib. on Instrum. Analysis, Beijing, 1987, p. 867.

  50. Z. L. Sun, M. C. Liu, Z. D. Hu, Bulletin of Analysis & testing5, 15 (1988);1, 1 (1989) (Chinese).

    Google Scholar 

  51. Z. L. Sun, G. Z. Dong, M. C. Liu, Z. D. Hu, Anal. Chem.5, 585 (1991) (Chinese).

    Google Scholar 

  52. Z. D. Hu, H. W. Zhang, J. Chromatogr. A,653, 275 (1993).

    Article  Google Scholar 

  53. A. F. M. Barton, CRC Handbook of Solubility Parameters and Other Cohesion Parameters, CRC Press, Inc. Boca Raton, Florida, 1983.

    Google Scholar 

  54. A. Tchapla, H. Colin, G. Guiochon, Anal. Chem.56, 621 (1984).

    Google Scholar 

  55. B. Rittich, S. Rudolfova, P. Jandera, Collet. Czech. Chem. Commun.55, 2138 (1990).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Applied Chemistry, Fushun Petroleum Institute, 113001, Liaoning Province, P. R. China

    Z. L. Sun

  2. Department of Chemistry, Lanzhou University, 730000, Gansu Province, P. R. China

    M. C. Liu & Z. D. Hu

Authors
  1. Z. L. Sun
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. C. Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Z. D. Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Sun, Z.L., Liu, M.C. & Hu, Z.D. Relationship between retention behavior and molecular structure in HPLC. Correlation between solubility parameter and molecular properties. Chromatographia 38, 599–608 (1994). https://doi.org/10.1007/BF02277161

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02277161

Key Words

Search

Navigation