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Phenomenon of dual- and single-retention behaviors of solutes and its validation by computational simulation in linear programmed temperature gas chromatography.

The current theory of programmed temperature gas chromatography considers that solutes are focused by the stationary phase at the column head completely and does not explicitly recognize the different effects of initial temperature (To ) and heating rate (rT ) on the retention time or temperature of a homologue series. In the present study, n-alkanes, 1-alkenes, 1-alkyl alcohols, alkyl benzenes, and fatty acid methyl esters standards were used as model chemicals and were separated on two nonpolar columns, one moderately polar column and one polar column. Effects of To and rT on the retention of nonstationary phase focusing solutes can be explicitly described with isothermal and cubic equation models, respectively. When the solutes were in the stationary phase focusing status, the single-retention behavior of solutes was observed. It is simple, dependent upon rT only and can be well described by the cubic equation model that was visualized through four sequential slope analyses. These observed dual- and single-retention behaviors of solutes were validated by various experimental data, physical properties, and computational simulation.