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Theory and practice of multiple headspace extraction

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Summary

Multiple headspace extraction (MHE) is an absolute quantitative method used in static headspace—GC. In principle it is dynamic gas extraction, carried out stepwise and establishing equilibrium conditions in each step. The concentration of the analyte in the headspace decreases exponentially during the series of extraction steps: by proper mathematical extrapolation the total peak area proportional to the total amount of analyte present in the original sample can be obtained.

This paper investigates MHE from the theoretical point of view using two approaches: a simplified theory regarding MHE as a first-order reaction, and a rigorous, step-by-step treatment of the MHE procedure. Special consideration is given to the fact that the headspace gas is only partially removed between individual steps. As shown, the results of both treatments are essentially the same hence the method is theoretically sound.

The practical limitations of MHE are also discussed pointing out how the analytical parameters may be adjusted to improve the possibility of determination by MHE.

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Abbreviations

a:

Slope of linear plot

A:

Peak area

A1 :

Peak area obtained in first headspace extraction

A2 :

Peak area obtained in second headspace extraction

Ai :

Peak area obtained in ith headspace extraction

An :

Peak area obtained in last headspace extraction

b:

y-Intercept of linear plot

c:

Concentration

c1 :

Initial concentration

ci :

Concentration of compound i

c *G1 :

Concentration of analyte in the headspace volume of the vial, at equilibrium, in the first MHE step

cG(1/2):

Concentration of analyte in the expanded volume of the headspace during venting

c *G2 :

Concentration of analyte in the headspace volume of the vial, at equilibrium, in the second MHE step

c *s1 :

Concentration of analyte in the sample present in the vial, at equilibrium, in the first MHE step

cs(1/2) :

Concentration of analyte in the sample present in vial, during venting

c *s2 :

Concentration of analyte in the sample present in the vial, at equilibrium, in the second MHE step

f:

Quotient of geometric progression

i:

Sequential number of a headspace extraction

K:

Distribution (partition) coefficient of analyte at equilibrium, at the thermostatting temperature (=c *s /c *G )

m1 :

Total amount of analyte present in the vial at the start of measurements

m1/2 :

Total amount of analyte remaining in the vial after venting

m2 :

Total amount of analytte in the vial in the second MHE step

m *G1 :

Amount of analyte in the headspace volume of the vial, at equilibrium, in the first MHE step

mG(1/2) :

Amount of analyte remaining in the headspace volume of the vial, after venting

m *G2 :

Amount of analyte in the headspace volume of the vial, at equilibrium, in the second MHE step

m *s1 :

Amount of analyte in the sample present in the vial, at equilibrium, in the first MHE step

m *s2 :

Amount of analyte in the sample present in the vial, at equilibrium, in the second MHE step

mv(1/2) :

Amount of analyte vented

n:

Sequential number of last headspace extraction

MHE:

Multiple headspace extraction

Pa :

Atmospheric pressure

Ph :

Pressure in the headspace of the vial in the first MHE step

Po :

Pressure in the headspace of the vial after venting

q:

Constant in the equation of first-order reaction

q′:

Constant in the MHE calculation according to the empirical theory

Q′:

Constant in the calculation of step-by-step investigation of MHE

t:

Time

VG :

Volume of the headspace (gas phase) in the vial

VG(1/2) :

Volume of the gas originally present in the headspace at Ph, after it expanded and now having the pressure of Po

VS :

Volume of sample in the vial

Vv1 :

Vented volume of the headspace

β:

Phase ratio of the vial (=VG/VS)

ρ:

Ratio of two pressures (=po/Ph)

*:

Asterisk refers to equilibrium conditions

References

  1. B. Kolb, M. Auer, P. Pospisil, Angewandte Chromatographie-Applied Chromatography, No.35E (1981), Bodenseewerk Perkin-Elmer & Co., Überlingen, FRG.

    Google Scholar 

  2. B. Kolb, M. Auer, Lebensmitt. Chem. Gerichtl. Chem.35, 92–94 (1981).

    CAS  Google Scholar 

  3. B. Kolb, Chromatographia15, 587–594 (1982).

    Article  CAS  Google Scholar 

  4. L. S. Ettre, E. Jones, B. S. Todd, Chromatogr. Newslett.12, 1–3 (1984).

    Google Scholar 

  5. B. Kolb, P. Pospisil, M. Auer, Chromatographia19, 113–122 (1984).

    CAS  Google Scholar 

  6. C. McAuliffe, Chem. Technol.1971, 46–51.

  7. C. McAuliffe, U. S. Pat. 3,759,086 (1973).

  8. M. Suzuki, S. Tsuge, T. Takeuchi, Anal. Chem.42, 1705–1708 (1970).

    CAS  Google Scholar 

  9. B. Kolb, P. Pospisil, Chromatographia10, 705–711 (1970).

    Google Scholar 

  10. A. Shinohara, A. Sato, N. Ishii, N. Onda, Chromatographia32, 357 (1991); a brief report was published in:K. Jinno, P. Sandra andT. Hanai (editors), Twelfth International Symposium on Capillary Chromatography (Kobe, Japan, September 11–14, 1990), Industrial Publishing & Consulting, Inc., Tokyo, Japan, 1990; pp. 151–157.

    CAS  Google Scholar 

  11. A. Venema, J. High Resolut. Chromatogr./Chromatogr. Commun.9, 637–649 (1986).

    Article  CAS  Google Scholar 

  12. A. Venema, J. High Resolut. Chromatogr./Chromatogr. Commun.11, 128–131 (1988).

    CAS  Google Scholar 

  13. A. Venema, J. High Resolut. Chromatogr./Chromatogr. Commun.13, 537–539 (1990).

    Article  CAS  Google Scholar 

  14. J. Gregoire, in:P. Sandra andW. Bertsch (editors), Sixth International Symposium on Capillary Chromatography (Riva del Garda, Italy, May 14–16, 1985), Huethig Verlag, Heidelberg, 1985; pp. 353–363.

    Google Scholar 

  15. L. S. Ettre, B. Kolb, Chromatographia32, 5–12 (1991).

    Article  CAS  Google Scholar 

  16. M. Ja. Wygodski, Elementarmathematik Griffbereit, Vieweg, Braunschweig, 1973; pp. 101–103.

    Google Scholar 

  17. A. G. Vitenberg, T. L. Reznik, J. Chromatogr.287, 15–27 (1984).

    Article  CAS  Google Scholar 

  18. F. A. Bencsath, K. Drysch, D. List, H. Weichardt, Angewandte Chromatographie-Applied Chromatography, No.32E (1978), Bodenseewerk Perkin-Elmer & Co., Überlingen, FRG.

    Google Scholar 

  19. B. Kolb, P. Pospisil, Chromatogr. Newslett.8, 35–37 (1980).

    CAS  Google Scholar 

  20. B. Kolb, M. Auer, Fresenius J. Anal. Chem.336, 297–302 (1990).

    CAS  Google Scholar 

  21. B. V. Ioffe, A. G. Vitenberg, Chromatographia11, 282–286 (1978)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Bodenseewerk Perkin-Elmer GmbH, 7770, Überlingen, Germany

    B. Kolb

  2. Department of Chemical Engineering, Yale University, P. O. Box 2159, 06520, Hew Haven, CT, USA

    L. S. Ettre

Authors
  1. B. Kolb
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  2. L. S. Ettre
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Kolb, B., Ettre, L.S. Theory and practice of multiple headspace extraction. Chromatographia 32, 505–513 (1991). https://doi.org/10.1007/BF02327895

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