Abstract

The effect of a gradient of solute velocity on the chromatographic separation of closely spaced solutes is investigated by usage of a simulation. The concept of the ideal basic separation (IBS), introduced by Blumberg, is used to determine the theoretical limit of a separation without any natural or artificial gradients of features of the chromatographic medium. The IBS is the best achievable separation and can therefore be used as a baseline to which other separations can be compared to. An addition of a negative velocity gradient cannot improve the separation of closely spaced solutes. The velocity gradient is realized by adding a temperature gradient to a GC separation. The simulation confirms this theoretical limit for a range of differently strong retained solutes.In a second part controlled deviations from IBS are used to show, that a velocity gradient can be beneficial in realistic, non-IBS. The addition of a negative velocity gradient can improve e.g. the separation of broad injected solute zones or counteract a positive gradient of the mobile phase velocity caused by gas decompression along the GC column. However, the improved separation cannot exceed that of a corresponding ideal basic separation. The resolution of broadly injected solutes can be increased by up to 45% of the corresponding IBS resolution by adding a negative velocity gradient. A positive velocity gradient due to gas decompression reduces the separation by up to 6%. The added negative velocity gradient, realized by a linear temperature gradient, can compensate this resolution loss by up to 2%.

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