Fractional distillation is a process by which components in a mixture are separated into different parts (called fractions) according to their different boiling points.
You use this when you can't use simple distillation – because the difference in boiling points are under 25 degrees C.
We use fractional distillation when we are trying to distill a liquid that has a boiling point less than 25 degrees C different than another. For example, we would use fractional distillation to separate two liquids with boiling points of 100 and 115, but not on two liquids with boiling points of 100 and 145.