Effect of signal noise on the determination of retention time of peak maximum. Computer simulation and experimental study

Summary

The effects of various sources of error on the measurement of the retention time of the peak maximum are studied. They include: the density of points of measurement, the signal-to-noise ratio, the width of the sequence used for the least-squares fit, and its out-centreness. The effect of these factors on the reproducibility and bias of the retention time measurements is derived by computer simulation. The results obtained are in excellent agreement with the experimental data if the contribution of the other sources of error is accounted for. The precision of the measurements of the retention time by the first moment or by the coordinates of the peak maximum is similar. Because of other contributions, especially deviation from linear response of the detector, the bias on the first moment is prone to be larger. Unfortunately, this is also the most meaningful parameter.