Fractional distillation is a process used to separate two liquids by the basis of their boiling points, which are generally within 30 °C of each other. As an example, consider the distillation of a mixture of water and ethanol. Ethanol boils at 78.4 °C while water boils at 100 °C. So, by heating the mixture, the most volatile component will concentrate to a greater degree in the vapor leaving the liquid. Some mixtures form azeotropes, where the mixture boils at a lower temperature than either component. In this example, a mixture of 96% ethanol and 4% water boils at 78.2 °C, being more volatile than pure ethanol. For this reason, ethanol cannot be completely purified by direct fractional distillation of ethanol-water mixtures. How to separate compounds using fractional distillation.
The apparatus is assembled as in the diagram. (The diagram represents a batch apparatus, as opposed to a continuous apparatus.) The mixture is put into the round bottomed flask along with a few anti-bumping granules (or a Teflon coated magnetic stirrer bar if using magnetic stirring), and the fractionating column is fitted into the top. The fractional distillation column is set up with the heat source at the bottom on the still pot. As the distance from the stillpot of the distillation column increases a heat gradient is formed in the column where it is coolest at top and hottest at the bottom. As the mixed vapor ascends the temperature gradient, some of the vapor condenses and revaporizes along the temperature gradient. Each time the vapor condenses and vaporizes, the composition of the more volatile liquid in the vapor increases. This distills the vapor along the length of the column, and eventually the vapor is composed solely of the more volatile liquid. The vapor condenses on the glass platforms, known as trays, inside the column, and runs back down into the liquid below, refluxing distillate. The efficiency in terms of the amount of heating and time required to get fractionation can be improved by insulating the outside of the column in an insulator such as wool, aluminium foil or preferably a vacuum jacket. The hottest tray is at the bottom and the coolest is at the top. At steady state conditions, the vapor and liquid on each tray are at equilibrium. Only the most volatile of the vapors stays in gaseous form all the way to the top. The vapor at the top of the column then passes into the condenser, which cools it down until it liquefies. The separation is more pure with the addition of more trays (to a practical limitation of heat, flow, etc.) The condensate that was initially very close to the azeotrope composition becomes gradually richer in water. The process continues until all the ethanol boils out of the mixture. This point can be recognized by the sharp rise in temperature shown on the thermometer.
Typically the example above now only reflects the theoretical way fractionation works. Normal laboratory fractionation columns will be simple glass tubes (often vacuum jacketed, and sometimes internally silvered) filled with a packing, often small glass helices of 4 to 7 mm diameter. Such a column can be calibrated by the distillation of a known mixture system to quantify the column in terms of number of theoretical plates. To improve fractionation the apparatus is set up to return condensate to the column by the use of some sort of reflux splitter (reflux wire, gago, Magnetic swinging bucket, etc.) - a typical careful fractionation would employ a reflux ratio of around 10:1 (10 parts returned condensate to 1 part condensate take off).
Separating compounds using fractional distillation in a laboratory, several types of condensers are commonly found. The Liebig condenser is simply a straight tube within a water jacket, and is the simplest (and relatively least expensive) form of condenser. The Graham condenser is a spiral tube within a water jacket, and the Allihn condenser has a series of large and small constrictions on the inside tube, each increasing the surface area upon which the vapor constituents may condense.