SummaryThe promising technique of controlling chromatographic selectivity by the adjustment of individual column temperatures in systems of series-coupled columns is investigated by means of a general model incorporating the effects of temperature and mobile phase compressibility. Expressions are derived for the linear flow velocity, the effective partition coefficient and the retention time for a system of n columns assuming an ideal mobile phase gas, under conditions of constant overall pressure drop and neglect of the temperature dependence of the mobile phase viscosity. The results indicate the importance of thermodynamic parameters, relative to parameters influencing the linear flow velocity, in determining the effect of temperature on the chromatographic retention time. Numerical results are illustrated graphically for two-column systems which are discussed in greater detail. Switching of columns is also discussed and it is shown that even if thermodynamic contributions remain unchanged, non-thermodynamic contributions have a noticeable effect.A characteristic feature of series-coupled columns, equipped with different stationary phases, is the possibility of controlling effective stationary phase properties of the combination by independent adjustment of individual column temperatures [1,2]. This configuration thus provides the chromatographer with knob-control of column selectivity. The usefulness of this facility is obvious and its practical applicability has been demonstrated recently [3] with the separation of the more important organophosphates in a single chromatogram.In a preliminary exploration of the theory of this technique, the basic phenomenological expressions for the effective partition coefficient, the retention time and the effective separation factor have been 'formulated [l]. However, no attempt has been made to relate these,quantities to the operating parameters of the chromatographic system. This paper, on the other hand, outlines a general description of series-coupled gas-chromatographic columns in termsof a model that incorporates most of the relevant chromatographic parameters with special emphasis on the effects of column temperature and compressibility of the mobile phase. The coaesponding expressions for the effective partition coefficient, the retention time and the linear flow velocity apply to any number of columns. Since in practice, however, dual columns appear to be the most likely situation, attention has been paid to the more important properties of two-column systems.
In a thorough investigation, Hildebrand and Reilley [4]derived similar expressions but did not consider the effect of column temperatures. The expressions derived in the present paper are new and it will be shown that the special case of equal column temperatures results in expressions similar to those of Hildebrand and Reilley.Switching of columns is also considered in this study in order to investigate the effects of both column ternperature and compressibility in conjunction with column order on the effec...