Modeling the combined effect of temperature and organic modifier content on reversed-phase chromatographic retention: Effectiveness of derived models in isocratic and isothermal mode retention prediction

Models considering simultaneously mobile phase organic content and column temperature were developed in this study by an extension of different equations describing the influence of temperature on solute retention. This extension was achieved by two methods: a semi-thermodynamic and a direct combination of equations expressed separately the dependence of the retention upon each of these factors. The above approaches gave a great number of expressions for the logarithm of the solute retention factor in terms of both temperature and organic content in the mobile phase, ln k(T,φ), determined from the dependence of the standard enthalpy of the retention process on T. From the final expressions of ln k(T,φ) we tested only those with the minimum number of adjustable parameters, i.e. those that correspond to a constant standard enthalpy of the retention process. For this test we examined the retention behaviour of a sample of alkylbenzenes in aqueous acetonitrile eluents. These compounds exhibit ln k versus 1/T plots with a very small curvature. We found that a new equation for ln k(T,φ) based on the adsorption model for retention performs better than all the others. The average percentage prediction error ranges from 0.7 to 1.4%.