Theory, chromatography overloading

Contemporary development of chromatography theory has tended to concentrate on dispersion in electro-chromatography and the treatment of column overload in preparative columns. Under overload conditions, the adsorption isotherm of the solute with respect to the stationary phase can be grossly nonlinear. One of the prime contributors in this research has been Guiochon and his co-workers, [27-30]. The form of the isotherm must be experimentally determined and, from the equilibrium data, and by the use of appropriate computer programs, it has been shown possible to calculate the theoretical profile of an overloaded peak. 

The theory of simple waves applies to large-volume injections, i.e., to the profiles obtained upon injection of rectangular profiles which are so wide that the injection plateau has not been entirely eroded when the band elutes. Then, simplifications of the solution occur because there is a constant state, the concentration plateau. This solution is not valid in overloaded elution chromatography when the injection volume is sufficiently small that the injection plateau has eroded and disappeared by the time the band elutes from the column. It is important to discuss this solution, however, because it takes a finite time for the profile of even a narrow rectangular injection to decay, and the band profile during that period is given by the simple wave solution. Also, this solution is the basis for a method of determination of competitive equilibrium isotherms (Chapter 4, Section 4.2.4). 

Courtesy of the Journal of Chromatography [ref. 1] Figure 1. Theory of Volume Column Overload... 

Preparative chromatography involves theory of some sort in almost every aspect, whether it is for calculation of the performance of a column to determine if it is sufficiently well packed for prolonged use or for a full optimisation. Very often calculations are made to determine the column and particle dimensions which allow operation of a separation at the maximum operating pressure of the equipment to maximise the production from the column. Overloading usually is more controllable if one knows the saturation capacity of the column, since this can allow at least approximate calculation of the appropriate load to try in a separation. Once the sample... 

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