When separating zeotropic mixtures with three or greater liquid components, each distillation column removes only the lowest-boiling point component and the highest boiling point component. In other words, each column separates two components purely. If three substances are separated with a single column, the substance with the intermediate boiling point will not be purely separated, and a second column would be needed. To separate mixtures consisting of multiple substances, a sequence of distillation columns must be used. This multi-step distillation process is also called rectification.
In each distillation column, pure components form at the top (rectifying section) and bottom (stripping section) of the column when the starting liquid (called feed composition) is released in the middle of the column. This is shown in Figure 2. At a certain temperature, the component with the lowest boiling point (called distillate or overhead fraction) vaporizes and collects at the top of the column, whereas the component with the highest boiling point (called bottoms or bottom fraction) collects at the bottom of the column. In a zeotropic mixture, where more than one component exists, individual components move relative to each other as vapor flows up and liquid falls down.
The separation of mixtures can be seen in a concentration profile. In a concentration profile, the position of a vapor in the distillation column is plotted against the concentration of the vapor. The component with the highest boiling point has a max concentration at the bottom of the column, where the component with the lowest boiling point has a max concentration at the top of the column. The component with the intermediate boiling point has a max concentration in the middle of the distillation column. Because of how these mixtures separate, mixtures with greater than three substances require more than one distillation column to separate the components.