Steam distillation vs Simple Distillation & Fractional Distillation

Question: What is the difference between steam

distillation, simple distillation and fractional distillation?
This is a very interesting question asked by one of my
students. As far as the syllabus is concerned, we only
need to concern ourselves with simple and fractional
distillation. As you are probably aware, the underlying
principle behind distillation is based on the difference in
the substances' boiling point. For example, simple
distillation is used to separate salt from water. However,
we should not forget that the reason why we are able to
distill off the water first is because water has a much lower
boiling point than salt. Recall that the chemical formula for
table salt is NaCl and it is an ionic compound which has a
relatively much higher boiling point. In short, simple
distillation is used when the boiling point of the concerned
substances vary significantly.
Fractional distillation is adopted when we need to separate
two miscible liquids i.e. ethanol and water. This technique
is commonly used if we need to separate two miscible
liquids that have very similar boiling points (less than 25
degree Celsius difference). Because of this, a fractionating
column is needed. In this method, heat is introduced to the
mixture until the boiling point of the more volatile solvent is
reached i.e. ethanol. The ethanol gas will then travel up
into the fractionating column. However, due to the close
proximity in boiling point of ethanol and water, the ethanol
gas may have contained some 'water contaminants'. After
all, evaporation takes place at all temperature. With the

supply of heat, it is not a surprise that some of the water

may have turned into water vapor at 78 degree Celsius,
thus 'contaminating' the ethanol vapor. The purpose of the
fractional column is to block the gas from rising further by
putting a large amount of 'obstacles' in its path, either by
using a series of trays/plates or by filling the column with
packing materials. What happens is that the rising gas will
condense on the tray/plates/packing materials and
become a liquid. Meanwhile, the rising gas from below will
heat this condensed liquid and cause it to be distilled
again. As a result, an even purer ethanol vapor will travel
up to the next level of the column. This process is
repeated continuously and eventually a pure ethanol vapor
is condensed and collected as the distillate.
However, there is one more hidden point about fractional
distillation that is not been told to us. That is, the two
miscible liquids must not be heat sensitive such that they
undergo decomposition fairly easily.
So far, I have not mentioned anything about steam
distillation yet =) Now, here comes the difficult part. What
happens if the liquid decomposes below its boiling point?
If that happens, then there is no way we can use simple or
fractional distillation at all because the liquid will already
have decomposed before it can be distilled off. Hey, wait a
minute! How can a substance decompose below its boiling
point? Boiling point is the temperature at which a liquid
turns to gas with the molecule'sintegrity intact isn't
it? With decomposition, the integrity of the molecule will
have been compromised. So, what are you talking about?

Let me explain. Boiling point is a variable that is

dependent on pressure. For instance, the boiling point of a
substance increases if the surrounding pressure increases
and vice versa. That is why our water boils at
approximately 80 degree Celsius when we are in the
Himalayan mountains. At high altitude, the surrounding
atmospheric pressure is lower. Thus, the water will boil at
a lower temperature. The boiling point that we are so
accustomed to is actually called the Normal Boiling
Point, where the atmospheric pressure is taken to be 1
atm. However, decomposition temperature is independent
of pressure. The decomposition temperature measures the
strength of the 'intra-molecular' force or chemical bond
within the molecule, whereas the boiling point measures
the strength of the 'inter-molecular' force between the
molecules. Let's take the example of H2O. Decomposition
temperature measures the amount of energy needed to
break the O-H bond i.e. the bond strength. Boiling point
measures the amount of energy needed to break the
intermolecular forces of attraction (also known as the
hydrogen bonding) between the water molecules and this
value is affected by the surrounding pressure.
Let's imagine liquid X decomposes when the temperature
hits 50 degree Celsius and it has a normal boiling point of
70 degree Celsius, say in Singapore which has a pressure
of 1 atm. If I were to bring liquid X to the Himalaya
mountains, it will have a lower boiling point of 40 degree
Celsius. What does this show? This shows that I can
perform fractional distillation on liquid X (its b.p is less than
its decomposition temperature and that of water) and

water because liquid X can be distilled off first without

undergoing decomposition. However, if I were to perform
the same technique on liquid X and water at 1 atm
pressure, say in Singapore, it will not be possible. This is
because liquid X will decompose first at 50 degree Celsius
before it can be distilled at its boiling point of 70 degree
Celsius!
To overcome this problem, steam distillation is used. It is
used to separate two miscible liquids which are highly heat
sensitive and may possibly decompose below their boiling
point. It is commonly used in the extraction of essential
oils.

Let's imagine the compounds to be distilled is

phenylamine (liquid X) and nitrobenzene (liquid Y). For my
'A' level students, do recall that phenylamine is obtained
via the reduction of nitrobenzene. Liquid X has a b.p of
184 degree Celsius while liquid Y has a b.p of 211 degree
Celsius. Although the difference in their boiling point
is approximately 25 degree Celsius, it is not advisable to
separate them by fractional distillation as these aromatic
compounds are usually quite heat sensitive. Instead,
steam is generated from the 1st bunsen burner and it is

passed through the compounds to be distilled. When the

steam touches the cool surface of the tube, it condenses
and heat is released. As a result, less heat is required
from the second bunsen burner. In addition, the pressure
inside the round bottom flask is low due to the low density
of steam. This means that the immiscible mixture will boil
at a lower temperature at a lower pressure. Instead of
boiling at 184 degree Celsius for liquid X, it is now boiled
at a lower temperature of 150 degree Celsius for instance
which enables it to be distilled off first. However, the
distillate collected will be a mixture of water (thanks to the
condensation of steam) and liquid X which can then be
separated using a separating funnel. Repeat the same
procedure to distill off liquid Y next.

The above diagram illustrates the same concept as

well.Good question and please keep the
questions coming!