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Mobile phase effects in reversed-phase chromatography VI. Thermodynamic models for retention and its dependence on mobile phase composition and temperature


The physico-chemical framework is examined by comparing the predictions of three models for the combined effects of the composition of the hydroorganic mobile phase and the column temperature on the retention ofn-alkylbenzenes on hydrocarbonaceous bonded stationary phases. The “well-mixed” model leads to expressions for the dependence of retention on three factors which are equivalent to those derived previously from linear extrathermodynamic relationships. The “diachoric” model stems from the assumption that the mobile phase is microscopically heterogeneous and the “displacement” model is identical to the retention model most widely used in chromatography with polar sorbents and less polar solvents. Over limited ranges of mobile phase composition and temperature, each model does describe retention behavior. However, only the wellmixed model describes retention well over the entire range of mobile phase composition and temperature studied here. The success of the well-mixed model, and its limits, give insight into the role of the organic solvent in determining the magnitude of chromatographic retention on non-polar stationary phases with hydro-organic eluents.

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Dedicated to Professor S. R. Lipsky on the occasion of his 60th birthday.

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Melander, W.R., Horváth, C. Mobile phase effects in reversed-phase chromatography VI. Thermodynamic models for retention and its dependence on mobile phase composition and temperature. Chromatographia 18, 353–361 (1984).

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Key Words

  • Retention mechanism
  • Reversed-phase chromatography
  • Retention thermodynamics
  • Mobile phase