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Determination of partition coefficients by automatic equilibrium headspace gas chromatography by vapor phase calibration

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Summary

Equilibrium headspace gas chromatography has been applied to the determination of the partition coefficients of volatile compounds in water-air systems. Only techniques that are suited to a fully automatic headspace procedure using the pneumatic headspace sampling-technique have been considered. Particularly simple is the technique of “vapor phase calibration —VPC” where an external vapor standard is used to calibrate the concentration of the volatile analyte in the headspace, while the concentration in the sample is found from the difference in the total amount in the vial. This technique is described in detail for 2-butanone in water. Finally, the water-air partition coefficients of several selected volatile compounds at different temperatures are listed together with their temperature functions.

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Abbreviations

AC :

Peak area of analyte from external vapor standard

AS :

Peak area of analyte from headspace sample

aC :

slope of regression of analyte from external vapor standard

aS :

slope of regression of analyte from sample vial

CS :

Concentration of analyte in sample

CG :

Concentration of analyte in gas phase of sample vial

CG C :

Vapor concentration of analyte in external vapor standard

K:

Partition coefficient

mo :

Total amount of analyte in vial

mG :

Amount of analyte in gas phase

mS :

Amount of analyte in sample

Pa :

Atmospheric pressure

Ph :

Headspace pressure in pressurized vial (Ph=Pa+PGC) with PGC as excess pressure given by pressure of GC

VG :

Volume of gas phase (headspace) in vial

VS :

Volume of sample in vial

VV :

Volume of headspace vial

β:

Phase ratio (β=VG/VS)

@:

Calibration factor

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Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday.

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Kolb, B., Welter, C. & Bichler, C. Determination of partition coefficients by automatic equilibrium headspace gas chromatography by vapor phase calibration. Chromatographia 34, 235–240 (1992). https://doi.org/10.1007/BF02268351

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  • DOI: https://doi.org/10.1007/BF02268351

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