DISTILLATION

CARLO B. GALICIA
Department of Chemical Engineering, College of Engineering and Architecture, Cebu Institute of Technology University, N.
Bacalso Ave. Cebu City, 6000 Philippines

Abstract
The separation of a liquid mixture into all or a part of its constituents
by heating the mixture and recovering the vapors by condensation is
known as distillation. The process depends upon differences in the vapor
pressures of the individual constituents: as the mixture is heated, vapors
are evolved which are relatively richer in the more volatile of the
constituents, i.e., those of lower boiling points, and, therefore, the
condensation of these vapors will give a product having a different com
position than that of the original mixture.
Obviously, the greater the difference in the vapor pressures of the
individual constituents, the greater will be the difference in their
concentrations in the vapor phase, and the easier will be the separation.
However, the degree of separation depends not only upon the properties
of the constituents but also upon the method employed in distilling the
mixture. Furthermore, as the number of constituents of the mixture
increases, the more difficult it becomes to effect their separation.
Therefore, most laboratory distillation experiments are performed with a
binary mixture.

1. Introduction
When two mutually soluble liquids are mixed, each component
lowers the vapor pressure of the other. For practically ideal solutions
at all concentrations, and for many non-ideal solutions at low
concentrations (dilute solutions), the extent of the lowering of the
vapor pressure can be determined from Raoult's law, which states
that at any given temperature the partial pressure of any
constituent in a mutually soluble liquid mixture is equal to the
product of its vapor pressure in the pure state and its mole fraction
in the solution. Mathematically, this relationship may be expressed
as

Raoult's law holds only for a mixture that is composed of liquids

that do not undergo chemical reaction or molecular association
when they are mixed, and whose molecules are approximately the
same size. Some mixtures, such as toluene and benzene, and
carbon tetrachloride and toluene, obey this law very closely over the
entire range of com position, but acetic acid and water, ethyl alcohol
and water, and many other common binary mixtures exhibit marked
deviations. According to Henry's law, the partial pressure of the
component that is present in the smallest concentration the solute
is proportional to its mole fraction in the solution.
Homogeneous binary mixtures may be classified into three
groups:
1. Mixtures with vapor pressures intermediate between those of
the pure constituents throughout the entire range of composition.
2. Mixtures with vapor pressures over a certain range of
composition greater than that of either of the pure constituents.
3. Mixtures with vapor pressures over a certain range of
composition lower than that of either of the pure constituents.
The equilibrium relationships between the liquid and vapor
phases of such mixtures can be represented graphically in several
different ways, but the most useful of these are the boiling-point and
the equilibrium diagrams.

Theory
Rectification: This is the most important of the distillation methods.
It involves the return of all or a part of the condensed vapors to the still in
such a manner that the vapors rising from the still come in intimate
contact with the downcoming liquid, known as reflux. The intimate contact
between the vapor and reflux results in a transfer of heat from the rising
vapor to the downcoming reflux, thereby causing the condensation of a
part of the less volatile component in the vapor and the vaporization of
the more volatile component in the reflux. As a result, the rising vapor
becomes enriched with the more volatile component, and separation is
materially increased. Rectification may be carried out as a batch process,
but continuous operation is much more common.
Objective
To determine the reflux ratio, required to recover ethanol of desired
specification from ethanol water mixture.

Materials & Equipment:

Distillation apparatus, Westphal balance, thermometer, water,
ethanol
Figure of the Set-up:

RECTIFICATION EQUIPMENT. The essential parts of a rectification

system are: (1) a still or kettle, (2) a column, and (3) a still head.
The Still. The still should be large enough to hold the desired quan
tity of charge and yet leave sufficient space to effectively separate the
vapors from the liquid. For very small laboratory units, the still is often
heated externally by electrical heaters, but for larger equipment the heat
is generally supplied by steam through coils in the still. For flexibility of
operation, multiple sets of heating coils may be provided, and to permit
the easy removal of the coils in the event that replacement becomes
necessary.
The Column. The column is generally a tall cylinder whose function
is to effect intimate contact between the rising vapor and the downcoming
stream of reflux; this is accomplished by the use of bubble-cap plates,
sieve plates, or a packing material. Bubble-Cap Columns. A bubble-cap
column consists of an upright shell containing a vertical series of
horizontal plates, which are generally spaced equally throughout the
length of the column. Each plate has one or more vapor pipes, which
provide a passage for the rising vapor, and a corresponding number of
bubble caps, which fit over the vapor pipes and deflect the vapor beneath
the surface of the liquid before it rises to the plate above.
The Still Head. That part of the distillation assembly above the
column is commonly referred to as the still head; this generally includes a
condenser, and some type of device for proportioning the condensate into
reflux and product.

The Condenser. The condenser may be designed to effect either

partial or total condensation of the vapors from the column. A partial
condenser, or dephlegmator, condenses only a portion of the vapors,
which are returned to the column as reflux; the rest of the vapors are
delivered to a final, or product, condenser. A total condenser, on the other
hand, condenses all of the .vapors, and the condensate is returned in total
or in part as reflux to the column. In general, a total condenser is
preferable because it requires less attention and it simplifies control of the
reflux.
Procedure
1. Check that all the vent lines provided are open.
2. Turn on the overhead condenser cooling water supply.
3. Charge the spherical vessel up to the equator with 30% by weight
ethanol solution.
4. Open the bypass around the steam trap and then carefully but
positively turn on the main steam supply, when the initial surge of
condensate has cleared, close the steam trap by-pass valve and
then set the steam pressure to a suitable pressure between 20 and
50 psig.
5. Set the reflux divider for the total reflux by closing the product offtake valve. When the liquid boils in the still the vapors pass up to
the column to the condenser. All the condensate will pass back to
the column.
6. Adjust the reboiler steam pressure to a value which gives adequate
loading on the packed column. This must not be less than 20 psig.
Give the unit time to settle down after each change in reboiler
steam pressure. Maintain this steam pressure for the duration of the
experiment.
7. Once the column has settled down to uniform operation under total
reflux, close the drain valve on, the lower product receiver, close the
valve between the product receivers.
8. Re-check that the vent valves on the product receivers and on the
overflow line to the still are open.
9. Fully open the product line valve by the reflux adapter and allow the
liquid in the adaptor to drain to the still. Close the recycle valve to
the still and then accurately measure the time to half fill the upper
product receiver. Close the product line valve and mark the level of
the liquid collected on the side of the receiver.
10.
Return the liquid in the cylinder to the still by introducing it
into the product recycle line to the still.
11.
With the valve between the product receivers closed and the
product recycle valve open three-quarters, open the product line

valve so as to give a positive reflux ratio. Adjust the valve setting if

the unit has no reflux to the column.
12.
Allow the column to settle down or at least 15 minutes.
13.
Close the product recycle valve and measure the time
required to fill the upper product receiver.
14.
Sample the product through the lower receiver. Measure the
temperature and specific gravity accurately.
15.
Re-open the product recycle valve.
16.
Repeat steps 11 to 15 with a higher reflux ratio achieved by
slightly closing the product line valve. Allow 15-20 minutes for the
column to settle down.
RESULTS
STEAM
PRESSURE
20 psia
30 psia
25 psia

TRIAL

t1

t2

1
2
1
2
1
2

20
18
17
19
18
17

26
22
23
24
22
21

0.3
0.22
0.35
0.26
0.22
0.24

CONCLUSIONS
As the concentration of the feed is increased, it is necessary to
increase the reflux rate to the distillation column. However, if the number
of stages is to be increased by increasing the number of plates, then the
reflux ratio could be minimized.