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Lattice-fluid model for gas-liquid chromatography.

Y Tao1, P S Wells, X Yi

  • 1Chemistry Department, University of Mississippi, University 38677, USA.

Journal of Chromatography. A
|December 10, 1999
PubMed
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The Sanchez and Lacombe lattice-fluid model accurately predicts chromatographic retention volumes for n-alkanes. This model also enables precise calculation of thermodynamic properties and solute size parameters without adjustable parameters.

Area of Science:

  • Physical Chemistry
  • Chromatography
  • Polymer Science

Background:

  • Lattice-fluid models simplify molecular behavior by considering occupied lattice sites and intermolecular interactions.
  • The Sanchez and Lacombe model is a key theoretical framework for understanding fluid thermodynamics.

Purpose of the Study:

  • To apply the Sanchez and Lacombe lattice-fluid model to predict specific retention volumes of n-alkanes in various stationary phases.
  • To derive theoretical equations for retention volume, its temperature dependence, and high-temperature limiting values.
  • To develop a novel chromatographic method for determining solute size parameters.

Main Methods:

  • Utilized the Sanchez and Lacombe lattice-fluid model.
  • Modeled specific retention volume data for n-alkane solutes.

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  • Employed n-alkane, polystyrene, and poly(dimethylsiloxane) as stationary liquid phases.
  • Derived theoretical equations for thermodynamic properties.

    • Main Results:

    • Predicted retention volumes within 10% for n-alkane phases, 22% for polystyrene, and 20-70% for PDMS, without adjustable parameters.
    • Calculated temperature derivatives (enthalpy) within 5% for all solute-phase systems.
    • Determined high-temperature limiting retention volumes within 10%.
    • Established a new method to measure solute size parameters (r) using stationary phase characteristics.

    Conclusions:

    • The lattice-fluid model provides accurate predictions for chromatographic retention and thermodynamic properties.
    • The model successfully determines solute size parameters independently of the stationary phase, validating experimental findings.
    • This approach offers a robust, parameter-free method for chromatographic analysis and molecular characterization.