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Comparative study on the thermodynamic retention models in HPLC

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Summary

A series of model substances with known solubility parameter were chromatographed and from the temperature dependence of the capacity factor, some of the thermodynamic parameters influencing solute retention were determined. A linear relationship was derived between the enthalpy density and the solute solubility parameter from which a graphical method was introduced for the determination of phase characteristics.

Comparing the predicted and measured capacity factor values it has been found that the predicted values are very sensitive to the literature data selected for the computation; however, by using the van der Waals molecular volume in the calculation significantly lower deviation was found from the measured data. Two equations are given for the prediction of selectivity and as the mathematical criteria of the validity of the used thermodynamic models. The results show that the predicted selectivity values are similar to the measured data using given initial parameters in the computation. However, the unreliability of the literature data makes the application of the retention models difficult.

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Dedicated to Professor J. F. K. Huber on the occasion of his 60th birthday.

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Szántó, J.I., Veress, T. Comparative study on the thermodynamic retention models in HPLC. Chromatographia 20, 596–600 (1985). https://doi.org/10.1007/BF02263218

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