Skip to main content
SpringerLink
Log in

Studies on external peak broadening in open-tubular liquid chromatography systems using the exponentially modified Gaussian model

  • Originals
  • Published:
Chromatographia Aims and scope Submit manuscript

Summary

To optimize performance in Open-Tubular Liquid Chromatography (OTLC) it is necessary to minimize external peak broadening. To see how to reduce the external broadening an insight into its origins is required. This can be obtained by careful evaluation of experimental results with peak deconvolution methods based on the exponentially modified Gaussian model and comparison with theoretical predictions. It is assumed that the column response is Gaussian and that the responses due to the external effects are exponential.

For peak deconvolution the algorithm described by Yau was used. Simulations were carried out to check the performance of the algorithm in calculating the standard deviation and the time constant. The effects of the presence of more than one time constant and of the number of data points and their position were investigated. The limits within which reliable results can be obtained are reported.

Experimental results were obtained with laser-induced fluorescence and mass spectrometric detection. It is shown that the Yau algorithm can be used to obtain physically realistic estimates of the contribution to peak distortion in the various system components. By suitable design external effects can be reduced to the order of 1 nl and in some cases even lower limits can be reached.

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.

Institutional subscriptions

Similar content being viewed by others

Abbreviations

A:

peak area

Fc :

column flow-rate

Fi :

split flow-rate

Fm :

make-up flow-rate

K:

injection profile factor (1–12)

Tr :

peak retention time

Vinj :

effective injection volume

Vchamber :

volume of a mixing chamber

σ:

peak standard deviation

σy :

peak standard deviation, calculated with the peak deconvolution program

σ 2tot :

total peak variance of a chromatographic peak

σ 2col :

peak variance due to the open tubular column

σ 2j :

peak variance due to a system component i.

τ:

overall time constant, as given by eq. (7)

τi :

time constant due to system component i.

τy :

overall time constant, calculated with the peak deconvolution program

References

  1. J. L. DiCesare, M. W. Dong, J. G. Atwood, J. Chromatogr.217, 369 (1981).

    Article  Google Scholar 

  2. R. P. W. Scott, C. F. Simpson, J. Chromatogr. Sci.20, 62 (1982).

    Google Scholar 

  3. F. Y. Yang, J. Chromatogr. Sci.20, 241 (1982).

    Google Scholar 

  4. J. C. Sternberg, Adv. Chromatogr.2, 205 (1966).

    Google Scholar 

  5. P. T. Kissinger, L. J. Felice, D. J. Miner, C. R. Preddy, R. E. Shoup, in ‘Contemporary topics in analytical and clinical chemistry’, vol. 2,D. M. Hercules, G. M. Hieftje, L. R. Snyder andM. A. Evenson, eds., Plenum Press, 1978, NY, USA; pag. 55–175.

    Google Scholar 

  6. M. Martin, C. Eon, G. Guiochon, J. Chromatogr.108, 229 (1975).

    Article  Google Scholar 

  7. H. Poppe, Anal. Chim. Acta114, 59 (1980).

    Article  Google Scholar 

  8. H. H. Lauer, G. P. Rozing, Chromatographia14, 641 (1981).

    Google Scholar 

  9. H. Poppe, Anal. Chim. Acta145, 17 (1983).

    Article  Google Scholar 

  10. K.-P. Hupe, R. J. Jonker, G. Rozing, J. Chromatogr.285, 253 (1984).

    Article  Google Scholar 

  11. V. Maynard, E. Grushka, Anal. Chem.44, 1427 (1972).

    Article  Google Scholar 

  12. R. E. Pauls, L. B. Rogers, Anal. Chem.49, 625 (1977).

    Article  Google Scholar 

  13. J. J. Kirkland, W. W. Yau, H. J. Stoklosa, C. H. Dilks Jr., J. Chromatogr. Sci.15, 303 (1977).

    PubMed  Google Scholar 

  14. H. P. M. van Vliet, H. Poppe, Submitted for publication.

  15. W. M. A. Niessen, H. Poppe, in preparation.

  16. W. M. A. Niessen, H. Poppe, J. Chromatogr.323, 37 (1985).

    Article  Google Scholar 

  17. J. H. Knox, M. T. Gilbert, J. Chromatogr.186, 405 (1979).

    Article  Google Scholar 

  18. J. P. Foley, J. G. Dorsey, J. Chromatogr. Sci.22, 40 (1984).

    Google Scholar 

  19. M. J. E. Golay, in ‘Gas Chromatography 1958’,D. H. Desty, ed., Butterworth, 1959, London, UK; pag. 36.

    Google Scholar 

  20. B. A. Bidlingmeyer, F. V. Warren, Jr, Anal. Chem.56, 1582A (1984).

    Article  Google Scholar 

  21. W. W. Yau, Anal. Chem.49, 395 (1977).

    Article  Google Scholar 

  22. E. Grushka, M. N. Myers, P. D. Schettler, J. C. Giddings, Anal. Chem.41, 889 (1969).

    Article  Google Scholar 

  23. J. P. Foley, J. G. Dorsey, Anal. Chem.55, 730 (1983).

    Article  Google Scholar 

  24. R. Delley, Chromatographia18, 374 (1984).

    Article  Google Scholar 

  25. D. J. Anderson, R. R. Walters, J. Chromatogr. Sci.22, 353 (1984).

    Google Scholar 

  26. H. P. M. van Vliet, W. M. A. Niessen, S. van der Linde, J. C. Kraak, H. Poppe, in preparation.

  27. H. P. M. van Vlieth, G. Bruin, J. C. Kraak, H. Poppe, in preparation.

Download references

Author information

Authors and Affiliations

  1. Laboratory for Analytical Chemistry, University of Amsterdam, Nieuwe Achtergracht 166, NL-1018 WV, Amsterdam, The Netherlands

    W. M. A. Niessen, H. P. M. van Vliet & H. Poppe

Authors
  1. W. M. A. Niessen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. H. P. M. van Vliet
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. H. Poppe
    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

Niessen, W.M.A., van Vliet, H.P.M. & Poppe, H. Studies on external peak broadening in open-tubular liquid chromatography systems using the exponentially modified Gaussian model. Chromatographia 20, 357–363 (1985). https://doi.org/10.1007/BF02269062

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02269062

Key Words

Search

Navigation