Error Sources in the Determination of Chromatographic Peak Size Ratios

Is it a problem to determine true peak sizes and peak size ratios? The reader may think the answer is, “no,” since today’s chromatographic separation systems are of excellent performance, and powerful integrators are on the market. However, let us take a closer look at the problem presented in Fig. 1. A peak pair with true areas of 1:4 or a ratio R of 0.250 needs to be analyzed. This value is unknown to the analyst. In (a), a column with 10,000 theoretical plates (N) giving symmetrical peaks (tailing T = 1.0) is used. The separation is performed without programming (i.e., under isocratic or isothermal conditions), and the chromatographic resolution obtained is 1.52. The integrator gives a peak area ratio of…