EXPERIMENTAL-VERIFICATION OF PARAMETERS CALCULATED WITH THE STATISTICAL-MODEL OF OVERLAP FROM CHROMATOGRAMS OF A SYNTHETIC MULTICOMPONENT MIXTURE

A synthetic mixture of 56 hydrocarbons was prepared and partially resolved by capillary gas chromatography to experimentally test the predictions of the statistical model of overlap. Various statistical parameters characteristic of both the mixture and the chromatographic process, Including the expected number of detectable mixture components and the expected numbers of singlet and multiplet chromatographic peaks, were theoretically estimated from several dozen chromatograms of this mixture by using two procedures. These theoretical parameters were then compared to their experimental counterparts, which were known for the synthetic mixture. Excellent agreement between experiment and theory was found at low chromatographic saturations. This agreement affirms earlier predictions based on this model and supports the argument that peak overlap can be addressed In some instances by theoretical means. At higher saturations, systematic departures of experiment from theory were found. In particular, the experimental numbers of singlet and multiplet peaks are smaller and larger, respectively, than those predicted, when the peak capacity is less than roughly twice the number of components. © 1990, American Chemical Society. All rights reserved.