A mixture of liquids rises and vapour condenses on glass beads/rods in the fractionating column. The temperature is lower towards the top of the column where the liquids condense and return to the flask. It then boils again and rises further up the column, increasing the amount of the lower boiling point liquid in the fractionating column which drips into the beaker. Once the temperature has exceeded the lower boiling point and approaches that of the higher boiling point liquid you swap the beakers out and collect the second liquid.