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Determination of gas-liquid partition coefficients by automatic equilibrium headspace-gas chromatography utilizing the phase ratio variation method

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Summary

The new phase ratio variation method is described which represents a convenient way for the determination of gas-liquid partition coefficients for practical purposes, utilizing equilibrium headspace-gas chromatography (EHS-GC). This method is based on the relationship between reciprocal peak area and the phase ratio in the vial containing the sample solution; it involves regression analysis of the EHS-GC measurements of a number of sample vials containing the same sample solution but with a wide variation of phase ratios. Examples are given for both aqueous systems and systems consisting of a stationary (liquid) phase used as the solvent; comparison of the measured values with results obtained by other methods shows satisfactory agreement. A critical discussion of the conditions influencing the accuracy of the analytical results is given.

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Abbreviations

EHS:

equilibrium headspace (sampling)

GC:

gas chromatography

GLPC:

gas-liquid partition chromatography

HS:

headspace (sampling)

MHE:

multiple headspace extraction

VPC:

vapor-phase calibration method for determination of the partition coefficient (EHS-GC)

a:

intercept of Eq. (20)

a′:

intercept of Eq. (27)

a″:

intercept of Eq. (30)

A:

peak area obtained when analyzing an aliquot of the gas phase (headspace) of the sample vial, in equilibrium with the sample (EHS-GC)

A1, A2 :

peak area obtained in EHS-GC measurements corresponding to vials with respective phase ratios of β1 and β2

b:

slope of Eq. (20)

b′:

slope of Eq. (27)

b″:

slope of Eq. (30)

c *G :

concentration of the analyte in the gas phase (headspace) of vial, at equilibrium (EHS)

c *L :

concentration of the analyte in the stationary (liquid) phase, at equilibrium

c *M :

concentration of the analyte in the mobile phase, at equilibrium

cS :

concentration of the analyte in the original sample (solution) in the sample vial (EHS)

c *S :

concentration of the analyte in the sample phase (solution) in the sample vial, at equilibrium (EHS)

fi :

proportionality factor

j:

carrier gas compressibility correction factor (GC)

k:

retention factor (capacity ratio) of the analyte

K:

partition coefficient (distribution constant) of the analyte

m *L :

amount of analyte present in the stationary (liquid) phase, at equilibrium

m *M :

amount of analyte present in the mobile phase, at equilibrium

r:

correlation coefficient of linear regression calculation

rc :

inner radius of the chromatographic column

tM :

hold-up time (retention time of a non-retained compound)

tR :

retention time of the analyte

t ′R :

adjusted retention time of the analyte

T:

absolute temperature

VG :

volume of the gas phase in the column (GC); volume of the gas phase (the headspace) in the sample vial (EHS)

VL :

volume of the stationary (liquid) phase in the chromatographic column

VM :

volume of the mobile phase in a chromatographic column in general; gas hold-up volume (retention volume of a non-retained compound) in GC)

VR :

retention volume of the analyte

V ′R :

adjusted retention volume of the analyte

VS :

volume of the sample solution introduced into the vial (EHS)

VV :

total volume of the vial (EHS)

WL :

amount of the stationary (liquid) phase in the column

β:

phase ratio of the chromatographic column (GC, LC); phase ratio of the sample vial (EHS)

β1, β1 :

maximum and minimum phase ratio values of a series of sample vials containing the same sample solution but in different volumes (EHS-GC)

πL :

density of the stationary (liquid) phase at column temperature

ΦS :

sample phase fraction in the headspace vial (EHS)

*:

asterisk refers to equilibrium conditions

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Authors and Affiliations

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

    L. S. Ettre

  2. Bodenseewerk Perkin-Elmer GmbH, D-7770, Überlingen, Germany

    C. Welter & B. Kolb

Authors
  1. L. S. Ettre
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  2. C. Welter
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  3. B. Kolb
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Additional information

Symbols which specifically refer to gas chromatography (GC), to equilibrium headspace sampling (EHS) and to EHS-GC are marked by the corresponding acronym.

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Ettre, L.S., Welter, C. & Kolb, B. Determination of gas-liquid partition coefficients by automatic equilibrium headspace-gas chromatography utilizing the phase ratio variation method. Chromatographia 35, 73–84 (1993). https://doi.org/10.1007/BF02278560

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  • DOI: https://doi.org/10.1007/BF02278560

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