Theory and application of the two-mode gradient elution in liquid chromatography involving simultaneous changes in temperature and mobile-phase composition

Anal Chem. 2008 Jul 15;80(14):5508-14. doi: 10.1021/ac800514m. Epub 2008 Jun 13.

Abstract

The theory of the dual-mode gradient elution in liquid chromatography involving any type of simultaneous changes in column temperature and mobile-phase composition is developed following Drake's approach. The theory was tested in the retention prediction of six alkylbenzenes in aqueous eluting systems modified by acetonitrile. Significant delay phenomena, i.e., a lag between the programmed gradient temperature and the temperature in the oven, and a lag between the oven temperature and the effective temperature the analyte feels in the column, were detected. When these phenomena were taken into account, the retention prediction obtained for all solutes under all dual-mode gradient conditions was excellent. The average percentage error between experimental and predicted retention times is below to 2%.