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Prediction of retention times of polycyclic aromatic hydrocarbons and n-alkanes in temperature-programmed gas chromatography

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Abstract

We have developed an iterative procedure for predicting the retention times of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes during separations by temperature-programmed gas chromatography. The procedure is based on estimates of two thermodynamic properties for each analyte (the differences in enthalpy and entropy associated with movements between the stationary and mobile phases) derived from data acquired experimentally in separations under isothermal conditions at temperatures spanning the range covered by the temperature programs in ten-degree increments. The columns used for this purpose were capillary columns containing polydimethylsiloxane-based stationary phases with three degrees of phenyl substitution (0%, 5%, and 50%). Predicted values were mostly within 1% of experimentally determined values, implying that the method is stable and precise.

Predicted values were mostly within 1 % of experimentally determined values, thus implying that the method is stable and precise

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Abbreviations

α :

Viscosity exponent

a 0 ...a 3 :

Distribution coefficient parameters

β :

Column phase ratio

ΔC p :

Isobaric heat capacity difference of analyte transfer

ΔG :

Molar free energy of solution

ΔH :

Enthalpy change of solution

ΔS :

Entropy change of solution

η :

Viscosity

i :

Time increment number

K :

Distribution coefficient

k′:

Retention factor

L :

Length of capillary column

N M :

Numbers of molecules of the analyte in the mobile phase

N S :

Numbers of molecules of the analyte in the stationary phase

P :

Inlet to outlet pressure ratio

p in :

Inlet pressure

p out :

Outlet pressure

r C :

Column radius

T :

Temperature

t :

Time

t M :

Hold-up time

t R :

Retention time

u :

Local velocity

u M :

Cross-sectional averaged axial velocity of the mobile phase

z :

Axial position in the column

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Authors and Affiliations

  1. Department of Analytical Chemistry, Stockholm University, 106 91, Stockholm, Sweden

    Fredrik Aldaeus, Yasar Thewalim & Anders Colmsjö

Authors
  1. Fredrik Aldaeus
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  2. Yasar Thewalim
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  3. Anders Colmsjö
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Correspondence to Anders Colmsjö.

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Aldaeus, F., Thewalim, Y. & Colmsjö, A. Prediction of retention times of polycyclic aromatic hydrocarbons and n-alkanes in temperature-programmed gas chromatography. Anal Bioanal Chem 389, 941–950 (2007). https://doi.org/10.1007/s00216-007-1528-0

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  • DOI: https://doi.org/10.1007/s00216-007-1528-0

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