Chromatographic quantitation using fractions of the peak areas

Quantitative chromatographic analysis is liable to errors due to peak asymmetry because the uncertainty in the detected position of the end of the peak tail decreases the reliability of the computed peak area. This dependence may be a severe drawback whenever peaks of different areas must be compared, as in the case of calibration curves. A new approach to overcome the uncertainties of area calculation due to peak asymmetry is reported in this paper. The approach consists of calculating only the area included between the start and the maximum of the chromatographic peak. Simulated and experimental chromatographic data were used in this study. Both the peak start-to-peak maximum area (SMA) and the start-to-end or total area (TA) were calculated and the quantitative results were compared. Within the scope of this work it is concluded that the SMA yields calibration curves that are more linear and have intercepts closer to zero than the calibration curves obtained using the TA.