New practical algorithm for modelling retention times in gradient reversed-phase high-performance liquid chromatography

Computer models have been widely used to predict the chromatographic behaviour of liquid chromatography systems. With the introduction of mass spectrometric detection and the use of lower mobile phase flow rates with conventional LC equipment, the influence of the dwell volume on the shape of the gradient curve becomes an issue in predicting the retention times. A new straight forward algorithm is proposed for the modelling of retention times in reversed-phase LC, taking the effect of the dwell volume on the gradient shape into account. The results show that the dwell volume has a large effect at lower flow rates and on the retention times of the analytes eluting at the end of fast gradient curves. The proposed model is able to make reliable predictions and can be helpful in LC–MS method development.